High-weight glyceride oligomers and methods of making the same

ABSTRACT

Oligomers of certain glyceride compounds are generally disclosed herein. In some embodiments, the glyceride compounds include natural oil glycerides, such as glycerides derived from natural oils, such as palm oil, soybean oil, canola oil, and the like. Compositions containing such glyceride oligomers are also disclosed herein. Processes for making such glyceride oligomers are also disclosed herein. In some embodiments, the processes for making such compounds include reacting a plurality of unsaturated glyceride compounds in the presence of a metathesis catalyst.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 15/239,830, filed Aug. 18, 2016, which is hereby incorporatedby reference as though set forth herein in its entirety.

TECHNICAL FIELD

Oligomers of certain glyceride compounds are disclosed herein. In someembodiments, the glyceride compounds include natural oil glycerides,such as glycerides of palm oil, soybean oil, canola oil, and the like.Compositions containing such glyceride oligomers are also disclosedherein. Processes for making such glyceride oligomers are also disclosedherein. In some embodiments, the processes for making such compoundsinclude reacting unsaturated glyceride compounds in the presence of anolefin metathesis catalyst.

BACKGROUND

Branched-chain polyesters have a wide variety of applications. Theirhigh molecular weight and low crystallinity makes them attractive foruse in adhesive compositions, personal and consumer care compositions,as plasticizers and rheology modifiers, and the like. Such compounds aretypically derived from certain short-chain dicarboxylic acids, such asadipic acid. Thus, such compounds may be unsuitable for certainapplications, especially where it may be desirable that the polyestercontain longer-chain hydrophobic portions.

The self-metathesis of natural oils, such as soybean oil, provides onemeans of making branched-chain polyesters having longer-chainhydrophobic portions. Certain such methods are disclosed in U.S. PatentApplication Publication No. 2013/0344012. But, using such methods, it isstill difficult to obtain branched-chain polyester compositions having ahigher molecular weight, such as molecular weights corresponding tooligomers containing, on average, about 5-6 triglycerides or more.Obtaining higher molecular-weight oligomers using such methods presentsa number of difficulties, including practical limits on the time and thequality of the vacuum needed to remove the product olefins to drive thereaction toward making higher-molecular-weight oligomers.

Thus, while using self-metathesis of natural oils provides a usefulmeans of obtaining branched-chain polyesters, there remains a continuingneed to develop processes that would allow for the practical synthesisof higher-weight glyceride oligomers.

SUMMARY

The present disclosure overcomes one or more of the above hurdles byproviding higher molecular-weight glyceride oligomers and processes formaking such compounds and compositions.

In a first aspect, the disclosure provides glyceride copolymers offormula (I):

wherein: R¹, R², R³, R⁴, and R⁵ are independently C₁₋₂₄ alkyl or C₂₋₂₄alkenyl, each of which is optionally substituted one or more times by—OH, or are independently an oligomeric glyceride moiety; X¹ and X² areindependently C₁₋₃₂ alkylene or C₂₋₃₂ alkenylene, each of which isoptionally substituted one or more times by —OH; two of G¹, G², and G³are —CH₂—, and one of G¹, G², and G³ is a direct bond; two of G⁴, G⁵,and G⁶ are —CH₂—, and one of G⁴, G⁵, and G⁶ is a direct bond; two of G⁷,G⁸, and G⁹ are —CH₂—, and one of G⁷, G⁸, and G⁹ is a direct bond; and nis an integer from 5 to 200; wherein the value X¹, R⁴, G⁴, G⁵, and G⁶for each repeating unit is selected independently of its value in otherrepeating units; and wherein if R¹ and R³, or R² and R⁵, or R³ and anadjacent R⁴, or R⁵ and an adjacent R⁴, or any two adjacent R⁴, are bothalkenyl groups, the two groups optionally combine via metathesis to forman alkenylene group.

In a second aspect, glyceride copolymers, which comprises constitutionalunits formed from reacting two or more monomers in the presence of ametathesis catalyst, the two or more monomers comprise monomer compoundsof formula (IIa):

and monomer compounds of formula (IIb):

wherein, R¹¹, R¹², and R¹³ are independently C₁₋₂₄ alkyl orC₂₋₂₄alkenyl, each of which is optionally substituted one or more timesby —OH, provided that at least one of R¹¹, R¹², and R¹³ is C₂₋₂₄alkenyl,which is optionally substituted one or more times by —OH; and R²¹, R²²,and R²³ are independently C₁₋₂₄ alkyl or C₂₋₂₄alkenyl, each of which isoptionally substituted one or more times by —OH.

In a third aspect, the disclosure provides glyceride copolymers, whichcomprises constitutional units formed from reacting two or more monomersin the presence of a first metathesis catalyst, the two or more monomerscomprise a first monomer and a second monomer; wherein the first monomeris a first unsaturated natural oil glyceride or an unsaturatedalkenylized natural oil glyceride, and the second monomer is anunsaturated alkenylized natural oil glyceride.

In a fourth aspect, the disclosure provides compositions comprisingglyceride copolymers of the first, second, and/or third aspects or anyembodiments thereof.

In a fifth aspect, the disclosure provides methods of forming aglyceride copolymer composition, the methods comprising: (a) providing areaction mixture comprising a metathesis catalyst and monomer compoundsof formula (IIIa):

and monomer compounds of formula (IIIb):

wherein, R³¹, R³², and R³³ are independently C₁₋₂₄ alkyl orC₂₋₂₄alkenyl, each of which is optionally substituted one or more timesby —OH, provided that at least one of R³¹, R³², and R³³ is C₂₋₂₄alkenyl,which is optionally substituted one or more times by —OH; and R⁴¹, R⁴²,and R⁴³ are independently C₁₋₂₄ alkyl or C₂₋₂₄alkenyl, each of which isoptionally substituted one or more times by —OH, provided that at leastone of R⁴¹, R⁴², and R⁴³ is 8-nonenyl, 8-decenyl, 8-undecenyl,8-dodecenyl, 8,11-dodecadienyl, 8,11-tridecadienyl,8,11-tetradecadienyl, 8,11-pentadecadienyl, 8,11,14-pentadecatrienyl,8,11,14-hexadecatrienyl, 8,11,14-heptadecatrienyl, or8,11,14-octadecatrienyl; and (b) reacting the monomer compounds offormula (IIIa) with the monomer compounds of formula (IIIb) in thepresence of the metathesis catalyst to form the glyceride polymercomposition.

In a sixth aspect, the disclosure provides methods of forming aglyceride copolymer, the methods comprising: (a) providing a reactionmixture comprising a first metathesis catalyst, unsaturated natural oilglycerides, and unsaturated alkenylized natural oil glycerides; and (b)reacting the unsaturated natural oil glycerides and unsaturatedalkenylized natural oil glycerides in the presence of the firstmetathesis catalyst to form the glyceride copolymer.

Further aspects and embodiments are provided in the foregoing drawings,detailed description and claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The following drawings are provided for purposes of illustrating variousembodiments of the compositions and methods disclosed herein. Thedrawings are provided for illustrative purposes only, and are notintended to describe any preferred compositions or preferred methods, orto serve as a source of any limitations on the scope of the claimedinventions.

FIG. 1 shows a glyceride copolymer of certain aspects and embodimentsdisclosed herein, wherein: R¹, R², R³, R⁴, and R⁵ are independentlyC₁₋₂₄ alkyl or C₂₋₂₄ alkenyl, each of which is optionally substituted,or are independently an oligomeric glyceride moiety; X¹ and X² areindependently C₁₋₃₂ alkylene or C₂₋₃₂ alkenylene, each of which isoptionally substituted; two of G¹, G², and G³ are —CH₂—, and one of G¹,G², and G³ is a direct bond; two of G⁴, G⁵, and G⁶ are —CH₂—, and one ofG⁴, G⁵, and G⁶ is a direct bond; two of G⁷, G⁸, and G⁹ are —CH₂—, andone of G⁷, G⁸, and G⁹ is a direct bond; and n is an integer from 5 to200; wherein the value X¹, R⁴, G⁴, G⁵, and G⁶ for each repeating unit isselected independently of its value in other repeating units; andwherein if R¹ and R³, or R² and R⁵, or R³ and an adjacent R⁴, or R⁵ andan adjacent R⁴, or any two adjacent R⁴, are both alkenyl groups, the twogroups optionally combine via metathesis to form an alkenylene group.

DETAILED DESCRIPTION

The following description recites various aspects and embodiments of theinventions disclosed herein. No particular embodiment is intended todefine the scope of the invention. Rather, the embodiments providenon-limiting examples of various compositions, and methods that areincluded within the scope of the claimed inventions. The description isto be read from the perspective of one of ordinary skill in the art.Therefore, information that is well known to the ordinarily skilledartisan is not necessarily included.

Definitions

The following terms and phrases have the meanings indicated below,unless otherwise provided herein. This disclosure may employ other termsand phrases not expressly defined herein. Such other terms and phrasesshall have the meanings that they would possess within the context ofthis disclosure to those of ordinary skill in the art. In someinstances, a term or phrase may be defined in the singular or plural. Insuch instances, it is understood that any term in the singular mayinclude its plural counterpart and vice versa, unless expresslyindicated to the contrary.

As used herein, the singular forms “a,” “an,” and “the” include pluralreferents unless the context clearly dictates otherwise. For example,reference to “a substituent” encompasses a single substituent as well astwo or more substituents, and the like.

As used herein, “for example,” “for instance,” “such as,” or “including”are meant to introduce examples that further clarify more generalsubject matter. Unless otherwise expressly indicated, such examples areprovided only as an aid for understanding embodiments illustrated in thepresent disclosure, and are not meant to be limiting in any fashion. Nordo these phrases indicate any kind of preference for the disclosedembodiment.

As used herein, “polymer” refers to a substance having a chemicalstructure that includes the multiple repetition of constitutional unitsformed from substances of comparatively low relative molecular massrelative to the molecular mass of the polymer. The term “polymer”includes soluble and/or fusible molecules having chains of repeat units,and also includes insoluble and infusible networks. As used herein, theterm “polymer” can include oligomeric materials, which have only a few(e.g., 3-100) constitutional units

As used herein, “natural oil” refers to oils obtained from plants oranimal sources. The terms also include modified plant or animal sources(e.g., genetically modified plant or animal sources), unless indicatedotherwise. Examples of natural oils include, but are not limited to,vegetable oils, algae oils, fish oils, animal fats, tall oils,derivatives of these oils, combinations of any of these oils, and thelike. Representative non-limiting examples of vegetable oils includerapeseed oil (canola oil), coconut oil, corn oil, cottonseed oil, oliveoil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil,sunflower oil, linseed oil, palm kernel oil, tung oil, jatropha oil,mustard seed oil, pennycress oil, camelina oil, hempseed oil, and castoroil. Representative non-limiting examples of animal fats include lard,tallow, poultry fat, yellow grease, and fish oil. Tall oils areby-products of wood pulp manufacture. In some embodiments, the naturaloil or natural oil feedstock comprises one or more unsaturatedglycerides (e.g., unsaturated triglycerides). In some such embodiments,the natural oil comprises at least 50% by weight, or at least 60% byweight, or at least 70% by weight, or at least 80% by weight, or atleast 90% by weight, or at least 95% by weight, or at least 97% byweight, or at least 99% by weight of one or more unsaturatedtriglycerides, based on the total weight of the natural oil.

The term “natural oil glyceride” refers to a glyceryl ester of a fattyacid obtained from a natural oil. Such glycerides includemonoacylglycerides, diacylglycerides, and triacylglyceriedes(triglycerides). In some embodiments, the natural oil glycerides aretriglycerides. Analogously, the term “unsaturated natural oil glyceride”refers to natural oil glycerides, wherein at least one of its fatty acidresidues contains unsaturation. For example, a glyceride of oleic acidis an unsaturated natural oil glyceride. The term “unsaturatedalkenylized natural oil glyceride” refers to an unsaturated natural oilglyceride (as defined above) that is derivatized via a metathesisreaction with a short-chain olefin (as defined below). In some cases,olefinizing process shortens one or more of the fatty acid chains in thecompound. For example, a glyceride of 9-decenoic acid is an unsaturatedalkenylized natural oil glyceride. Similarly, butenylized (e.g., with1-butene and/or 2-butene) canola oil is a natural oil glyceride that hasbeen modified via metathesis to contain some short-chain unsaturatedC₁₀-C₁₅ ester groups.

The term “oligomeric glyceride moiety” is a moiety comprising two ormore (and up to 10, or up to 20) constitutional units formed via olefinmetathesis from natural oil glycerides and/or alkenylized natural oilglycerides.

As used herein, “metathesis” refers to olefin metathesis. As usedherein, “metathesis catalyst” includes any catalyst or catalyst systemthat catalyzes an olefin metathesis reaction.

As used herein, “metathesize” or “metathesizing” refer to the reactingof a feedstock in the presence of a metathesis catalyst to form a“metathesized product” comprising new olefinic compounds, i.e.,“metathesized” compounds. Metathesizing is not limited to any particulartype of olefin metathesis, and may refer to cross-metathesis (i.e.,co-metathesis), self-metathesis, ring-opening metathesis, ring-openingmetathesis polymerizations (“ROMP”), ring-closing metathesis (“RCM”),and acyclic diene metathesis (“ADMET”). In some embodiments,metathesizing refers to reacting two triglycerides present in a naturalfeedstock (self-metathesis) in the presence of a metathesis catalyst,wherein each triglyceride has an unsaturated carbon-carbon double bond,thereby forming a new mixture of olefins and esters which may include atriglyceride dimer. Such triglyceride dimers may have more than oneolefinic bond, thus higher oligomers also may form. Additionally, insome other embodiments, metathesizing may refer to reacting an olefin,such as ethylene, and a triglyceride in a natural feedstock having atleast one unsaturated carbon-carbon double bond, thereby forming newolefinic molecules as well as new ester molecules (cross-metathesis).

As used herein, “olefin” or “olefins” refer to compounds having at leastone unsaturated carbon-carbon double bond. In certain embodiments, theterm “olefins” refers to a group of unsaturated carbon-carbon doublebond compounds with different carbon lengths. Unless noted otherwise,the terms “olefin” or “olefins” encompasses “polyunsaturated olefins” or“poly-olefins,” which have more than one carbon-carbon double bond. Asused herein, the term “monounsaturated olefins” or “mono-olefins” refersto compounds having only one carbon-carbon double bond. A compoundhaving a terminal carbon-carbon double bond can be referred to as a“terminal olefin” or an “alpha-olefin,” while an olefin having anon-terminal carbon-carbon double bond can be referred to as an“internal olefin.” In some embodiments, the alpha-olefin is a terminalalkene, which is an alkene (as defined below) having a terminalcarbon-carbon double bond. Additional carbon-carbon double bonds can bepresent.

The number of carbon atoms in any group or compound can be representedby the terms: “C_(z)”, which refers to a group of compound having zcarbon atoms; and “C_(x-y)”, which refers to a group or compoundcontaining from x to y, inclusive, carbon atoms. For example,“C₁₋₆alkyl” represents an alkyl chain having from 1 to 6 carbon atomsand, for example, includes, but is not limited to, methyl, ethyl,n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl,isopentyl, n-pentyl, neopentyl, and n-hexyl. As a further example, a“C₄₋₁₀alkene” refers to an alkene molecule having from 4 to 10 carbonatoms, and, for example, includes, but is not limited to, 1-butene,2-butene, isobutene, 1-pentene, 1-hexene, 3-hexene, 1-heptene,3-heptene, 1-octene, 4-octene, 1-nonene, 4-nonene, and 1-decene.

As used herein, the terms “short-chain alkene” or “short-chain olefin”refer to any one or combination of unsaturated straight, branched, orcyclic hydrocarbons in the C₂₋₁₄ range, or the C₂₋₁₂ range, or the C₂₋₁₀range, or the C₂₋₈ range. Such olefins include alpha-olefins, whereinthe unsaturated carbon-carbon bond is present at one end of thecompound. Such olefins also include diener or trienes. Such olefins alsoinclude internal olefins. Examples of short-chain alkenes in the C₂₋₆range include, but are not limited to: ethylene, propylene, 1-butene,2-butene, isobutene, 1-pentene, 2-pentene, 2-methyl-1-butene,2-methyl-2-butene, 3-methyl-1-butene, cyclopentene, 1,4-pentadiene,1-hexene, 2-hexene, 3-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene,4-methyl-2-pentene, 2-methyl-3-pentene, and cyclohexene. Non-limitingexamples of short-chain alkenes in the C₇₋₉ range include1,4-heptadiene, 1-heptene, 3,6-nonadiene, 3-nonene, 1,4,7-octatriene. Incertain embodiments, it is preferable to use a mixture of olefins, themixture comprising linear and branched low-molecular-weight olefins inthe C₄₋₁₀ range. In one embodiments, it may be preferable to use amixture of linear and branched C₄ olefins (i.e., combinations of:1-butene, 2-butene, and/or isobutene). In other embodiments, a higherrange of C₁₁₋₁₄ may be used.

As used herein, “alkyl” refers to a straight or branched chain saturatedhydrocarbon having 1 to 30 carbon atoms, which may be optionallysubstituted, as herein further described, with multiple degrees ofsubstitution being allowed. Examples of “alkyl,” as used herein,include, but are not limited to, methyl, ethyl, n-propyl, isopropyl,isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl, n-pentyl,neopentyl, n-hexyl, and 2-ethylhexyl. The number of carbon atoms in analkyl group is represented by the phrase “C_(x-y)alkyl,” which refers toan alkyl group, as herein defined, containing from x toy, inclusive,carbon atoms. Thus, “C₁₋₆alkyl” represents an alkyl chain having from 1to 6 carbon atoms and, for example, includes, but is not limited to,methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl,tert-butyl, isopentyl, n-pentyl, neopentyl, and n-hexyl. In someinstances, the “alkyl” group can be divalent, in which case the groupcan alternatively be referred to as an “alkylene” group.

As used herein, “alkenyl” refers to a straight or branched chainnon-aromatic hydrocarbon having 2 to 30 carbon atoms and having one ormore carbon-carbon double bonds, which may be optionally substituted, asherein further described, with multiple degrees of substitution beingallowed. Examples of “alkenyl,” as used herein, include, but are notlimited to, ethenyl, 2-propenyl, 2-butenyl, and 3-butenyl. The number ofcarbon atoms in an alkenyl group is represented by the phrase“C_(x-y)alkenyl,” which refers to an alkenyl group, as herein defined,containing from x to y, inclusive, carbon atoms. Thus, “C₂₋₆ alkenyl”represents an alkenyl chain having from 2 to 6 carbon atoms and, forexample, includes, but is not limited to, ethenyl, 2-propenyl,2-butenyl, and 3-butenyl. In some instances, the “alkenyl” group can bedivalent, in which case the group can alternatively be referred to as an“alkenylene” group.

As used herein, “direct bond” refers to an embodiment where theidentified moiety is absent from the structure, and is replaced by abond between other moieties to which it is connected. For example, ifthe specification or claims recite A-D-E and D is defined as a directbond, the resulting structure is A-E.

As used herein, “substituted” refers to substitution of one or morehydrogen atoms of the designated moiety with the named substituent orsubstituents, multiple degrees of substitution being allowed unlessotherwise stated, provided that the substitution results in a stable orchemically feasible compound. A stable compound or chemically feasiblecompound is one in which the chemical structure is not substantiallyaltered when kept at a temperature from about −80° C. to about +40° C.,in the absence of moisture or other chemically reactive conditions, forat least a week. As used herein, the phrases “substituted with one ormore . . . ” or “substituted one or more times . . . ” refer to a numberof substituents that equals from one to the maximum number ofsubstituents possible based on the number of available bonding sites,provided that the above conditions of stability and chemical feasibilityare met.

As used herein, “mix” or “mixed” or “mixture” refers broadly to anycombining of two or more compositions. The two or more compositions neednot have the same physical state; thus, solids can be “mixed” withliquids, e.g., to form a slurry, suspension, or solution. Further, theseterms do not require any degree of homogeneity or uniformity ofcomposition. This, such “mixtures” can be homogeneous or heterogeneous,or can be uniform or non-uniform. Further, the terms do not require theuse of any particular equipment to carry out the mixing, such as anindustrial mixer.

As used herein, “optionally” means that the subsequently describedevent(s) may or may not occur. In some embodiments, the optional eventdoes not occur. In some other embodiments, the optional event does occurone or more times.

As used herein, “comprise” or “comprises” or “comprising” or “comprisedof” refer to groups that are open, meaning that the group can includeadditional members in addition to those expressly recited. For example,the phrase, “comprises A” means that A must be present, but that othermembers can be present too. The terms “include,” “have,” and “composedof” and their grammatical variants have the same meaning. In contrast,“consist of” or “consists of” or “consisting of” refer to groups thatare closed. For example, the phrase “consists of A” means that A andonly A is present.

As used herein, “or” is to be given its broadest reasonableinterpretation, and is not to be limited to an either/or construction.Thus, the phrase “comprising A or B” means that A can be present and notB, or that B is present and not A, or that A and B are both present.Further, if A, for example, defines a class that can have multiplemembers, e.g., A₁ and A₂, then one or more members of the class can bepresent concurrently.

In some instances herein, organic compounds are described using the“line structure” methodology, where chemical bonds are indicated by aline, where the carbon atoms are not expressly labeled, and where thehydrogen atoms covalently bound to carbon (or the C—H bonds) are notshown at all. For example, by that convention, the formula

represents n-propane. In some instances herein, a squiggly bond is usedto show the compound can have any one of two or more isomers. Forexample, the structure

can refer to (E)-2-butene or (Z)-2-butene. The same is true whenolefinic structures are drawn that are ambiguous as to which isomer isreferred to. For example, CH₃—CH═CH—CH₃ can refer to (E)-2-butene or(Z)-2-butene.

As used herein, the various functional groups represented will beunderstood to have a point of attachment at the functional group havingthe hyphen or dash (—) or an asterisk (*). In other words, in the caseof —CH₂CH₂CH₃, it will be understood that the point of attachment is theCH₂ group at the far left. If a group is recited without an asterisk ora dash, then the attachment point is indicated by the plain and ordinarymeaning of the recited group.

As used herein, multi-atom bivalent species are to be read from left toright. For example, if the specification or claims recite A-D-E and D isdefined as —OC(O)—, the resulting group with D replaced is: A-OC(O)-Eand not A-C(O)O-E.

Other terms are defined in other portions of this description, eventhough not included in this subsection.

Glyceride Oligomers

In one aspect, the disclosure provides glyceride copolymers of formula(I):

wherein: R¹, R², R³, R⁴, and R⁵ are independently C₁₋₂₄ alkyl or C₂₋₂₄alkenyl, each of which is optionally substituted one or more times by—OH, or are independently an oligomeric glyceride moiety; X¹ and X² areindependently C₁₋₃₂ alkylene or C₂₋₃₂ alkenylene, each of which isoptionally substituted one or more times by —OH; two of G¹, G², and G³are —CH₂—, and one of G¹, G², and G³ is a direct bond; two of G⁴, G⁵,and G⁶ are —CH₂—, and one of G⁴, G⁵, and G⁶ is a direct bond; two of G²,G⁸, and G⁹ are —CH₂—, and one of G², G⁸, and G⁹ is a direct bond; and nis an integer from 5 to 200; wherein the value X¹, R⁴, G⁴, G⁵, and G⁶for each repeating unit is selected independently of its value in otherrepeating units; and wherein if R¹ and R³, or R² and R⁵, or R³ and anadjacent R⁴, or R⁵ and an adjacent R⁴, or any two adjacent R⁴, are bothalkenyl groups, the two groups optionally combine via metathesis to forman alkenylene group.

G¹, G², and G³ can have any suitable value. In some embodiments, G¹ andG² are —CH₂— and G³ is a direct bond. In some other embodiments, G¹ andG³ are —CH₂— and G² is a direct bond. In some other embodiments, G² andG³ are —CH₂— and G¹ is a direct bond.

G⁴, G⁵, and G⁶ can, in each instance, independently have any suitablevalue. In some embodiments of any of the aforementioned embodiments, inat least one instance, G⁴ and G⁵ are —CH₂— and G⁶ is a direct bond. Insome other embodiments of any of the aforementioned embodiments, in atleast one instance, G⁴ and G⁶ are —CH₂— and G⁵ is a direct bond. In someother embodiments of any of the aforementioned embodiments, in at leastone instance, G⁵ and G⁶ are —CH₂— and G⁴ is a direct bond.

G², G⁸, and G⁹ can have any suitable value. In some embodiments of anyof the aforementioned embodiments, G⁷ and G⁸ are —CH₂— and G⁹ is adirect bond. In some other embodiments of any of the aforementionedembodiments, G⁷ and G⁹ are —CH₂— and G⁸ is a direct bond. In some otherembodiments of any of the aforementioned embodiments, G⁸ and G⁹ are—CH₂— and G⁷ is a direct bond.

X¹ can have any suitable value. In some embodiments of any of theaforementioned embodiments, X¹ is —(CH₂)₁₆—, —(CH₂)₁₈—, —(CH₂)₁₉—,—(CH₂)₂₀—, —(CH₂)₂₂—, —(CH₂)₂₅—, —(CH₂)₂₈—, —(CH₂)₇—CH═CH—(CH₂)₇—,—(CH₂)₉—CH═CH—(CH₂)₇—, —(CH₂)₇—CH═CH—(CH₂)₉—, —(CH₂)₁₁—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—(CH₂)₁₁—, —(CH₂)₇—CH═CH—CH₂—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—, or—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—. In somesuch embodiments, X¹ is —(CH₂)₁₆—, —(CH₂)₁₈—, —(CH₂)₁₉—, —(CH₂)₂₂—,—(CH₂)₂₅—, —(CH₂)₂₈—, —(CH₂)₇—CH═CH—(CH₂)₇—, —(CH₂)₉—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—(CH₂)₉—, —(CH₂)₇—CH═CH—CH₂—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—, or—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—. In somesuch embodiments, X¹ is —(CH₂)₁₆—, —(CH₂)₁₉—, —(CH₂)₂₂—, —(CH₂)₂₅—,—(CH₂)₂₈—, —(CH₂)₇—CH═CH—(CH₂)₇—, —(CH₂)₇—CH═CH—CH₂—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—, or—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—. In somefurther such embodiments, X¹ is —(CH₂)₇—CH═CH—(CH₂)₇—,—(CH₂)₉—CH═CH—(CH₂)₇—, —(CH₂)₇—CH═CH—(CH₂)₉—,—(CH₂)₇—CH═CH—CH₂—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—, or—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—. In somefurther such embodiments, X¹ is —(CH₂)₇—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—CH₂—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—, or—(CH₂)₇—CH═CH—CH_(Z)—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—.

X² can have any suitable value. In some embodiments of any of theaforementioned embodiments, X² is —(CH₂)₁₆—, —(CH₂)₁₈—, —(CH₂)₁₉—,—(CH₂)₂₀—, —(CH₂)₂₂—, —(CH₂)₂₅—, —(CH₂)₂₈—, —(CH₂)₇—CH═CH—(CH₂)₇—,—(CH₂)₉—CH═CH—(CH₂)₇—, —(CH₂)₂—CH═CH—(CH₂)₉—, —(CH₂)₁₁—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—(CH₂)₁₁—, —(CH₂)₇—CH═CH—CH₂—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—, or—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—. In somesuch embodiments, X² is —(CH₂)₁₆—, —(CH₂)₁₈—, —(CH₂)₁₉—, —(CH₂)₂₂—,—(CH₂)₂₅—, —(CH₂)₂₈—, —(CH₂)₇—CH═CH—(CH₂)₇—, —(CH₂)₉—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—(CH₂)₉—, —(CH₂)₇—CH═CH—CH₂—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—, or—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—. In somesuch embodiments, X² is —(CH₂)₁₆—, —(CH₂)₁₉—, —(CH₂)₂₂—, —(CH₂)₂₅—,—(CH₂)₂₈—, —(CH₂)₇—CH═CH—(CH₂)₇—, —(CH₂)₇—CH═CH—CH₂—CH═CH—(CH₂)₇—,—(CH₂)₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—, or—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—. In somefurther such embodiments, X² is —(CH₂)₇—CH═CH—(CH₂)₇—,—(CH₂)₉—CH═CH—(CH₂)₇—, —(CH₂)₇—CH═CH—(CH₂)₉—,—(CH₂)₇—CH═CH—CH₂—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—, or—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—. In somefurther such embodiments, X² is —(CH₂)₇—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—CH₂—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—,—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—, or—(CH₂)₇—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—.

R¹ can have any suitable value. In some embodiments of any of theaforementioned embodiments, R¹ is C₁₋₂₄ alkyl, or C₁₁₋₂₄ alkyl, orC₁₃₋₂₄ alkyl, or C₁₅₋₂₄ alkyl. In some such embodiments, R¹ is undecyl,tridecyl, pentadecyl, or heptadecyl. In some further such embodiments,R¹ is pentadecyl or heptadecyl. In some embodiments of any of theaforementioned embodiments, R¹ is C₂₋₂₄ alkenyl or C₉₋₂₄ alkenyl. Insome such embodiments, R¹ is 8-heptadecenyl, 10-heptadecenyl,12-heneicosenyl, 8,11-heptadecadienyl, 8,11,14-heptadecatrienyl,8-nonenyl, 8-decenyl, 8-undecenyl, 10-undecenyl, 8-dodecenyl,8,11-dodecadienyl, 8,11-tridecadienyl, 8,11-tetradecadienyl,8,11-pentadecadienyl, 8,11,14-pentadecatrienyl, 8,11,14-hexadecatrienyl,8,11,14-heptadecatrienyl, or 8,11,14-octadecatrienyl. In some furthersuch embodiments, R¹ is 8-heptadecenyl, 10-heptadecenyl,8,11-heptadecadienyl, or 8,11,14-heptadecatrienyl. In some further suchembodiments, R¹ is 8-heptadecenyl, 8,11-heptadecadienyl, or8,11,14-heptadecatrienyl. In some such embodiments, R¹ is 8-nonenyl,8-decenyl, 8-undecenyl, 10-undecenyl, 8-dodecenyl, 8,11-dodecadienyl,8,11-tridecadienyl, 12-tridecenyl, 8,11-tetradecadienyl,8,11-pentadecadienyl, 8,11,14-pentadecatrienyl, 8,11,14-hexadecatrienyl,8,11,14-heptadecatrienyl, or 8,11,14-octadecatrienyl. In some furthersuch embodiments, R¹ is 8-nonenyl, 8-decenyl, 8-undecenyl, 8-dodecenyl,8,11-dodecadienyl, 8,11-tridecadienyl, 8,11-tetradecadienyl,8,11-pentadecadienyl, 8,11,14-pentadecatrienyl, 8,11,14-hexadecatrienyl,8,11,14-heptadecatrienyl, or 8,11,14-octadecatrienyl. In some furthersuch embodiments, R¹ is 8-nonenyl, 8-undecenyl, 8,11-dodecadienyl,8,11-tetradecadienyl, or 8,11,14-pentadecatrienyl. In some embodiments,R¹ is an oligomeric glyceride moiety.

R² can have any suitable value. In some embodiments of any of theaforementioned embodiments, R² is C₁₋₂₄ alkyl, or C₁₁₋₂₄ alkyl, orC₁₃₋₂₄ alkyl, or C₁₅₋₂₄ alkyl. In some such embodiments, R² is undecyl,tridecyl, pentadecyl, or heptadecyl. In some further such embodiments,R² is pentadecyl or heptadecyl. In some embodiments of any of theaforementioned embodiments, R² is C₂₋₂₄ alkenyl or C₉₋₂₄ alkenyl. Insome such embodiments, R² is 8-heptadecenyl, 10-heptadecenyl,12-heneicosenyl, 8,11-heptadecadienyl, 8,11,14-heptadecatrienyl,8-nonenyl, 8-decenyl, 8-undecenyl, 10-undecenyl, 8-dodecenyl,8,11-dodecadienyl, 8,11-tridecadienyl, 8,11-tetradecadienyl,8,11-pentadecadienyl, 8,11,14-pentadecatrienyl, 8,11,14-hexadecatrienyl,8,11,14-heptadecatrienyl, or 8,11,14-octadecatrienyl. In some furthersuch embodiments, R² is 8-heptadecenyl, 10-heptadecenyl,8,11-heptadecadienyl, or 8,11,14-heptadecatrienyl. In some further suchembodiments, R² is 8-heptadecenyl, 8,11-heptadecadienyl, or8,11,14-heptadecatrienyl. In some such embodiments, R² is 8-nonenyl,8-decenyl, 8-undecenyl, 10-undecenyl, 8-dodecenyl, 8,11-dodecadienyl,8,11-tridecadienyl, 8,11-tetradecadienyl, 8,11-pentadecadienyl,8,11,14-pentadecatrienyl, 8,11,14-hexadecatrienyl,8,11,14-heptadecatrienyl, or 8,11,14-octadecatrienyl. In some furthersuch embodiments, R² is 8-nonenyl, 8-decenyl, 8-undecenyl, 8-dodecenyl,8,11-dodecadienyl, 8,11-tridecadienyl, 12-tridecenyl,8,11-tetradecadienyl, 8,11-pentadecadienyl, 8,11,14-pentadecatrienyl,8,11,14-hexadecatrienyl, 8,11,14-heptadecatrienyl, or8,11,14-octadecatrienyl. In some further such embodiments, R² is8-nonenyl, 8-undecenyl, 8,11-dodecadienyl, 8,11-tetradecadienyl, or8,11,14-pentadecatrienyl. In some embodiments, R² is an oligomericglyceride moiety.

R³ can have any suitable value. In some embodiments of any of theaforementioned embodiments, R³ is C₁₋₂₄ alkyl, or C₁₁₋₂₄ alkyl, orC₁₃₋₂₄ alkyl, or C₁₅₋₂₄ alkyl. In some such embodiments, R³ is undecyl,tridecyl, pentadecyl, or heptadecyl. In some further such embodiments,R³ is pentadecyl or heptadecyl. In some embodiments of any of theaforementioned embodiments, R³ is C₂₋₂₄ alkenyl or C₉₋₂₄ alkenyl. Insome such embodiments, R³ is 8-heptadecenyl, 10-heptadecenyl,12-heneicosenyl, 8,11-heptadecadienyl, 8,11,14-heptadecatrienyl,8-nonenyl, 8-decenyl, 8-undecenyl, 10-undecenyl, 8-dodecenyl,8,11-dodecadienyl, 8,11-tridecadienyl, 8,11-tetradecadienyl,8,11-pentadecadienyl, 8,11,14-pentadecatrienyl, 8,11,14-hexadecatrienyl,8,11,14-heptadecatrienyl, or 8,11,14-octadecatrienyl. In some furthersuch embodiments, R³ is 8-heptadecenyl, 10-heptadecenyl,8,11-heptadecadienyl, or 8,11,14-heptadecatrienyl. In some further suchembodiments, R³ is 8-heptadecenyl, 8,11-heptadecadienyl, or8,11,14-heptadecatrienyl. In some such embodiments, R³ is 8-nonenyl,8-decenyl, 8-undecenyl, 10-undecenyl, 8-dodecenyl, 8,11-dodecadienyl,8,11-tridecadienyl, 8,11-tetradecadienyl, 8,11-pentadecadienyl,8,11,14-pentadecatrienyl, 8,11,14-hexadecatrienyl,8,11,14-heptadecatrienyl, or 8,11,14-octadecatrienyl. In some furthersuch embodiments, R³ is 8-nonenyl, 8-decenyl, 8-undecenyl, 8-dodecenyl,8,11-dodecadienyl, 8,11-tridecadienyl, 12-tridecenyl,8,11-tetradecadienyl, 8,11-pentadecadienyl, 8,11,14-pentadecatrienyl,8,11,14-hexadecatrienyl, 8,11,14-heptadecatrienyl, or8,11,14-octadecatrienyl. In some further such embodiments, R³ is8-nonenyl, 8-undecenyl, 8,11-dodecadienyl, 8,11-tetradecadienyl, or8,11,14-pentadecatrienyl. In some embodiments, R³ is an oligomericglyceride moiety.

R⁴ can, in each of its instances, have any suitable value. In someembodiments of any of the aforementioned embodiments, R⁴, in at leastone instance, is C₁₋₂₄ alkyl, or C₁₁₋₂₄ alkyl, or C₁₃₋₂₄ alkyl, orC₁₅₋₂₄ alkyl. In some such embodiments, R⁴ is, in at least one instance,undecyl, tridecyl, pentadecyl, or heptadecyl. In some further suchembodiments, R⁴ is, in at least one instance, pentadecyl or heptadecyl.In some embodiments of any of the aforementioned embodiments, R⁴ is, inat least one instance, C₂₋₂₄ alkenyl or C₉₋₂₄ alkenyl. In some suchembodiments, R⁴ is, in at least one instance, 8-heptadecenyl,10-heptadecenyl, 12-heneicosenyl, 8,11-heptadecadienyl,8,11,14-heptadecatrienyl, 8-nonenyl, 8-decenyl, 8-undecenyl,10-undecenyl, 8-dodecenyl, 8,11-dodecadienyl, 8,11-tridecadienyl,8,11-tetradecadienyl, 8,11-pentadecadienyl, 8,11,14-pentadecatrienyl,8,11,14-hexadecatrienyl, 8,11,14-heptadecatrienyl, or8,11,14-octadecatrienyl. In some further such embodiments, R⁴ is, in atleast one instance, 8-heptadecenyl, 10-heptadecenyl,8,11-heptadecadienyl, or 8,11,14-heptadecatrienyl. In some further suchembodiments, R⁴ is, in at least one instance, 8-heptadecenyl,8,11-heptadecadienyl, or 8,11,14-heptadecatrienyl. In some suchembodiments, R⁴ is, in at least one instance, 8-nonenyl, 8-decenyl,8-undecenyl, 10-undecenyl, 8-dodecenyl, 8,11-dodecadienyl,8,11-tridecadienyl, 12-tridecenyl, 8,11-tetradecadienyl,8,11-pentadecadienyl, 8,11,14-pentadecatrienyl, 8,11,14-hexadecatrienyl,8,11,14-heptadecatrienyl, or 8,11,14-octadecatrienyl. In some furthersuch embodiments, R⁴ is, in at least one instance, 8-nonenyl, 8-decenyl,8-undecenyl, 8-dodecenyl, 8,11-dodecadienyl, 8,11-tridecadienyl,8,11-tetradecadienyl, 8,11-pentadecadienyl, 8,11,14-pentadecatrienyl,8,11,14-hexadecatrienyl, 8,11,14-heptadecatrienyl, or8,11,14-octadecatrienyl. In some further such embodiments, R⁴ is, in atleast one instance, 8-nonenyl, 8-undecenyl, 8,11-dodecadienyl,8,11-tetradecadienyl, or 8,11,14-pentadecatrienyl. In some embodiments,R⁴, in at least one instance, is an oligomeric glyceride moiety.

R⁵ can have any suitable value. In some embodiments of any of theaforementioned embodiments, R⁵ is C₁₋₂₄ alkyl, or C₁₁₋₂₄ alkyl, orC₁₃₋₂₄ alkyl, or C₁₅₋₂₄ alkyl. In some such embodiments, R⁵ is undecyl,tridecyl, pentadecyl, or heptadecyl. In some further such embodiments,R⁵ is pentadecyl or heptadecyl. In some embodiments of any of theaforementioned embodiments, R⁵ is C₂₋₂₄ alkenyl or C₉₋₂₄ alkenyl. Insome such embodiments, R⁵ is 8-heptadecenyl, 10-heptadecenyl,12-heneicosenyl, 8,11-heptadecadienyl, 8,11,14-heptadecatrienyl,8-nonenyl, 8-decenyl, 8-undecenyl, 10-undecenyl, 8-dodecenyl,8,11-dodecadienyl, 8,11-tridecadienyl, 8,11-tetradecadienyl,8,11-pentadecadienyl, 8,11,14-pentadecatrienyl, 8,11,14-hexadecatrienyl,8,11,14-heptadecatrienyl, or 8,11,14-octadecatrienyl. In some furthersuch embodiments, R⁵ is 8-heptadecenyl, 10-heptadecenyl,8,11-heptadecadienyl, or 8,11,14-heptadecatrienyl. In some further suchembodiments, R⁵ is 8-heptadecenyl, 8,11-heptadecadienyl, or8,11,14-heptadecatrienyl. In some such embodiments, R⁵ is 8-nonenyl,8-decenyl, 8-undecenyl, 10-undecenyl, 8-dodecenyl, 8,11-dodecadienyl,12-tridecenyl, 8,11-tridecadienyl, 8,11-tetradecadienyl,8,11-pentadecadienyl, 8,11,14-pentadecatrienyl, 8,11,14-hexadecatrienyl,8,11,14-heptadecatrienyl, or 8,11,14-octadecatrienyl. In some furthersuch embodiments, R⁵ is 8-nonenyl, 8-decenyl, 8-undecenyl, 8-dodecenyl,8,11-dodecadienyl, 8,11-tridecadienyl, 8,11-tetradecadienyl,8,11-pentadecadienyl, 8,11,14-pentadecatrienyl, 8,11,14-hexadecatrienyl,8,11,14-heptadecatrienyl, or 8,11,14-octadecatrienyl. In some furthersuch embodiments, R⁵ is 8-nonenyl, 8-undecenyl, 8,11-dodecadienyl,8,11-tetradecadienyl, or 8,11,14-pentadecatrienyl. In some embodiments,R⁵ is an oligomeric glyceride moiety.

The variable n can have any suitable value. In some embodiments of anyof the aforementioned embodiments, n is an integer from 7 to 100, orfrom 10 to 60, or from 12 to 40. In some other embodiments, n is aninteger from 5 to 30, or from 7 to 25, or from 10 to 20.

In some embodiments of any of the aforementioned embodiments, theglyceride polymers include only compounds wherein at least one of R¹,R², R³, and R⁵, or at least one instance of R⁴, is selected from thegroup consisting of: 8-nonenyl; 8-decenyl; 8-undecenyl; 10-undecenyl,12-tridecenyl; 8-dodecenyl; 8,11-dodecadienyl; 8,11-tridecadienyl;8,11-tetradecadienyl; 8,11-pentadecadienyl; 8,11,14-pentadecatrienyl;8,11,14-hexadecatrienyl; 8,11,14-heptadecatrienyl; and8,11,14-octadecatrienyl. In some other embodiments of any of theaforementioned embodiments, the glyceride polymers include onlycompounds wherein at least one of R¹, R², R³, and R⁵, or at least oneinstance of R⁴, is selected from the group consisting of: 8-nonenyl;8-decenyl; 8-undecenyl; 8-dodecenyl; 8,11-dodecadienyl;8,11-tridecadienyl; 8,11-tetradecadienyl; 8,11-pentadecadienyl;8,11,14-pentadecatrienyl; 8,11,14-hexadecatrienyl;8,11,14-heptadecatrienyl; and 8,11,14-octadecatrienyl. In some otherembodiments of any of the aforementioned embodiments, the glyceridepolymers include only compounds wherein at least one of R¹, R², R³, andR⁵, or at least one instance of R⁴, is selected from the groupconsisting of: 8-nonenyl; 8-undecenyl; 8,11-dodecadienyl;8,11-tetradecadienyl; or 8,11,14-pentadecatrienyl. In some embodimentsof any of the aforementioned embodiments, the glyceride polymers includeonly compounds wherein at least one of R¹, R², R³, and R⁵, or at leastone instance of R⁴, is selected from the group consisting of: 8-nonenyl;8-decenyl; 8-undecenyl; 10-undecenyl; 12-tridecenyl; 8-dodecenyl;8,11-dodecadienyl; 8,11-tridecadienyl; 8,11-tetradecadienyl;8,11-pentadecadienyl; 8,11,14-pentadecatrienyl; and8,11,14-hexadecatrienyl. In some other embodiments of any of theaforementioned embodiments, the glyceride polymers include onlycompounds wherein at least one of R¹, R², R³, and R⁵, or at least oneinstance of R⁴, is selected from the group consisting of: 8-nonenyl;8-decenyl; 8-undecenyl; 8-dodecenyl; 8,11-dodecadienyl;8,11-tridecadienyl; 8,11-tetradecadienyl; 8,11-pentadecadienyl;8,11,14-pentadecatrienyl; and 8,11,14-hexadecatrienyl. In some otherembodiments of any of the aforementioned embodiments, the glyceridepolymers include only compounds wherein at least one of R¹, R², R³, andR⁵, or at least one instance of R⁴, is C₂₋₁₅ alkenyl, or C₂₋₁₄ alkenyl,or C₅₋₁₄ alkenyl, or C₂₋₁₃ alkenyl, or C₂₋₁₂ alkenyl, or C₅₋₁₂ alkenyl.

In a another aspect, glyceride copolymers, which comprisesconstitutional units formed from reacting two or more monomers in thepresence of a metathesis catalyst, the two or more monomers comprisemonomer compounds of formula (IIa):

and monomer compounds of formula (IIb):

wherein, R¹¹, R¹² and R¹³ are independently C₁₋₂₄ alkyl or C₂₋₂₄alkenyl,each of which is optionally substituted one or more times by —OH,provided that at least one of R¹¹, R¹², and R¹³ is C₂₋₂₄alkenyl, whichis optionally substituted one or more times by —OH; and R²¹, R²², andR²³ are independently C₁₋₂₄ alkyl or C₂₋₂₄alkenyl, each of which isoptionally substituted one or more times by —OH.

The variables R¹¹, R¹² and R¹³ can have any suitable value. In someembodiments, R¹¹, R¹², and R¹³ are independently C₁₋₂₄ alkyl, or C₁₁₋₂₄alkyl, or C₁₃₋₂₄ alkyl, or C₁₅₋₂₄ alkyl. In some such embodiments, R¹¹,R¹², and R¹³ are independently undecyl, tridecyl, pentadecyl, orheptadecyl. In some further such embodiments, R¹¹, R¹², and R¹³ areindependently pentadecyl or heptadecyl. In some embodiments of any ofthe aforementioned embodiments, R¹¹, R¹² and R¹³ are independently C₂₋₂₄alkenyl, or C₉₋₂₄ alkenyl, or C₁₁₋₂₄ alkenyl, or C₁₃₋₂₄ alkenyl, orC₁₅₋₂₄ alkenyl. In some such embodiments, R¹¹, R¹², and R¹³ areindependently 8-heptadecenyl, 10-heptadecenyl, 8,11-heptadecadienyl or8,11,14-heptadecatrienyl. In some further such embodiments, R¹¹, R¹²,and R¹³ are independently 8-heptadecenyl, 8,11-heptadecadienyl, or8,11,14-heptadecatrienyl.

The variables R²¹, R²², and R²³ can have any suitable value. In someembodiments of any of the foregoing embodiments, zero, one, or two ofR²¹, R²², and R²³ are independently C₁₋₂₄ alkyl, or C₁₁₋₂₄ alkyl, orC₁₃₋₂₄ alkyl, or C₁₅₋₂₄ alkyl. In some such embodiments, zero, one, ortwo of R²¹, R²², and R²³ are independently undecyl, tridecyl,pentadecyl, or heptadecyl. In some further such embodiments, zero, one,or two of R²¹, R²², and R²³ are independently pentadecyl or heptadecyl.In some embodiments of any of the aforementioned embodiments, zero, one,or two of R²¹, R²², and R²³ are independently C₂₋₂₄ alkenyl, or C₉₋₂₄alkenyl, or C₁₁₋₂₄ alkenyl, or C₁₃₋₂₄ alkenyl, or C₁₅₋₂₄ alkenyl. Insome such embodiments, zero, one, or two of R²¹, R²², and R²³ areindependently 8-heptadecenyl, 10-heptadecenyl, 8,11-heptadecadienyl or8,11,14-heptadecatrienyl. In some further such embodiments, zero, one,or two of R²¹, R²², and R²³ are independently 8-heptadecenyl,8,11-heptadecadienyl, or 8,11,14-heptadecatrienyl.

In some other embodiments of any of the foregoing embodiments, one, two,or three of R²¹, R²², and R²³ are independently C₂₋₁₅ alkenyl, or C₂₋₁₄alkenyl, C₅₋₁₄ alkenyl, or C₂₋₁₃ alkenyl, or C₂₋₁₂ alkenyl, or C₅₋₁₂alkenyl. In some such embodiments, one, two, or three of R²¹, R²², andR²³ are independently 8-nonenyl, 8-decenyl, 8-undecenyl, 10-undecenyl,12-tridecenyl, 8-dodecenyl, 8,11-dodecadienyl, 8,11-tridecadienyl,8,11-tetradecadienyl, 8,11-pentadecadienyl, 8,11,14-pentadecatrienyl,8,11,14-hexadecatrienyl, 8,11,14-heptadecatrienyl, or8,11,14-octadecatrienyl. In some further such embodiments, one, two, orthree of R²¹, R²², and R²³ are independently 8-nonenyl, 8-decenyl,8-undecenyl, 8-dodecenyl, 8,11-dodecadienyl, 8,11-tridecadienyl,8,11-tetradecadienyl, 8,11-pentadecadienyl, 8,11,14-pentadecatrienyl,8,11,14-hexadecatrienyl, 8,11,14-heptadecatrienyl, or8,11,14-octadecatrienyl. In some further such embodiments, one, two, orthree of R²¹, R²², and R²³ are independently 8-nonenyl, 8-undecenyl,8,11-dodecadienyl, 8,11-tetradecadienyl, or 8,11,14-pentadecatrienyl.

The glyceride copolymers disclosed herein can have any suitablemolecular weight. In some embodiments of any of the aforementionedembodiments, the glyceride copolymer has a molecular weight ranging from4,000 g/mol to 150,000 g/mol, or from 5,000 g/mol to 130,000 g/mol, orfrom 6,000 g/mol to 100,000 g/mol, or from 7,000 g/mol to 50,000 g/mol,or from 8,000 g/mol to 30,000 g/mol, or from 9,000 g/mol to 20,000g/mol.

The glyceride copolymers disclosed herein can have any suitable ratio ofconstitutional units formed from monomer compounds of formula (IIa) toconstitutional units formed from monomer compounds of formula (IIb). Insome embodiments of any of the aforementioned embodiments, the numberratio of constitutional units formed from monomer compounds of formula(IIa) to constitutional units formed from monomer compounds of formula(IIb) is no more than 10:1, or no more than 9:1, or no more than 8:1, orno more than 7:1, or no more than 6:1, or no more than 5:1, or no morethan 4:1, or no more than 3:1, or no more than 2:1, or no more than 1:1.The glyceride copolymers disclosed herein can include additionalconstitutional units not formed from monomer compounds of either formula(IIa) or formula (IIb), including, but not limited to, constitutionalunits formed from other unsaturated polyol esters, such as unsaturateddiols, triols, and the like.

Or, in some other embodiments of any of the foregoing embodiments, thetwo or more monomers are reacted in the presence of the metathesiscatalyst as part of a reaction mixture, wherein the weight-to-weightratio of the monomer compounds of formula (IIa) to the monomer compoundsof formula (IIb) in the reaction mixture is no more than 10:1, or nomore than 9:1, or no more than 8:1, or no more than 7:1, or no more than6:1, or no more than 5:1, or no more than 4:1, or no more than 3:1, orno more than 2:1, or no more than 1:1. In some embodiments, the reactionmixture includes additional monomer compounds besides monomer compoundsof formula (IIa) and formula (IIb).

Any suitable metathesis catalyst can be used, as described in moredetail below. In some embodiments of any of the aforementionedembodiments, the metathesis catalyst is an organoruthenium compound, anorganoosmium compound, an organotungsten compound, or anorganomolybdenum compound.

In a another aspect, the disclosure provides glyceride copolymers, whichcomprises constitutional units formed from reacting two or more monomersin the presence of a first metathesis catalyst, the two or more monomerscomprise a first monomer and a second monomer; wherein the first monomeris a first unsaturated natural oil glyceride, and the second monomer isan unsaturated alkenylized natural oil glyceride.

In some embodiments, the unsaturated alkenylized natural oil glycerideis formed from the reaction of a second unsaturated natural oilglyceride with a short-chain alkene in the presence of a secondmetathesis catalyst. In some such embodiments, the unsaturatedalkenylized natural oil glyceride has a lower molecular weight than thesecond unsaturated natural oil glyceride. Any suitable short-chainalkene can be used, according to the embodiments described above. Insome embodiments, the short-chain alkene is a C₂₋₈ olefin, or a C₂₋₆olefin. In some such embodiments, the short-chain alkene is ethylene,propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene,1-hexene, 2-hexene, or 3-hexene. In some further such embodiments, theshort-chain alkene is ethylene, propylene, 1-butene, 2-butene, orisobutene. In some embodiments, the short-chain alkene is ethylene. Insome embodiments, the short-chain alkene is propylene. In someembodiments, the short-chain alkene is 1-butene. In some embodiments,the short-chain alkene is 2-butene. In some other embodiments, theshort-chain alkene is a branched short-chain alkene. Non-limitingexamples of such branched short-chain alkenes include, but are notlimited to, isobutylene, 3-methyl-1-butene, 3-methyl-1-pentene, and4-methyl-1-pentene.

The first unsaturated natural oil glyceride and the second unsaturatednatural oil glyceride can be obtained from any suitable natural oilsource. In some embodiments of any of the aforementioned embodiments,the first or second unsaturated natural oil glycerides are obtained froma vegetable oil, such as a seed oil. In some further embodiments, thevegetable oil is rapeseed oil, canola oil (low erucic acid rapeseedoil), coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanutoil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil,palm kernel oil, tung oil, jatropha oil, mustard seed oil, pennycressoil, camelina oil, hempseed oil, or castor oil. In some embodiments, thevegetable oil is palm oil. In some embodiments, the vegetable oil issoybean oil. In some embodiments, the vegetable oil is canola oil.

The glyceride copolymers disclosed herein can have any suitablemolecular weight. In some embodiments of any of the aforementionedembodiments, the glyceride copolymer has a molecular weight ranging from4,000 g/mol to 150,000 g/mol, or from 5,000 g/mol to 130,000 g/mol, orfrom 6,000 g/mol to 100,000 g/mol, or from 7,000 g/mol to 50,000 g/mol,or from 8,000 g/mol to 30,000 g/mol, or from 9,000 g/mol to 20,000g/mol.

The glyceride copolymers disclosed herein can have any suitable ratio ofconstitutional units formed from the first monomer to constitutionalunits formed from the second monomer. In some embodiments of any of theaforementioned embodiments, the number ratio of constitutional unitsformed from the first monomer to constitutional units formed from thesecond monomer is no more than 10:1, or no more than 9:1, or no morethan 8:1, or no more than 7:1, or no more than 6:1, or no more than 5:1,or no more than 4:1, or no more than 3:1, or no more than 2:1, or nomore than 1:1. The glyceride copolymers disclosed herein can includeadditional constitutional units not formed from the first monomer or thesecond monomer, including, but not limited to, constitutional unitsformed from other unsaturated polyol esters, such as unsaturated diols,triols, and the like.

Or, in some other embodiments of any of the foregoing embodiments, thetwo or more monomers are reacted in the presence of the metathesiscatalyst as part of a reaction mixture, wherein the weight-to-weightratio of the first monomer to the second monomer in the reaction mixtureis no more than 10:1, or no more than 9:1, or no more than 8:1, or nomore than 7:1, or no more than 6:1, or no more than 5:1, or no more than4:1, or no more than 3:1, or no more than 2:1, or no more than 1:1. Insome embodiments, the reaction mixture includes additional monomercompounds besides the first monomer and the second monomer.

Any suitable metathesis catalyst can be used as either the firstmetathesis catalyst or the second metathesis catalyst, as described inmore detail below. In some embodiments of any of the aforementionedembodiments, the first and second metathesis catalysts are anorganoruthenium compound, an organoosmium compound, an organotungstencompound, or an organomolybdenum compound.

Additional glyceride copolymers are contemplated as products of thesynthetic methods and examples disclosed herein.

Glyceride Oligomer Compositions

In another aspect, the disclosure provides compositions comprising oneor more glyceride copolymers of any of the foregoing aspects andembodiments thereof.

In some embodiments, the composition can contain glyceride copolymershaving a range of molecular weights. Thus, in some embodiments, thenumber-average molecular weight (M_(n)) of the one or more glyceridecopolymers in the composition ranges from 4,000 g/mol to 150,000 g/mol,or from 5,000 g/mol to 30,000 g/mol, or from 6,000 g/mol to 20,000g/mol. In some embodiments, the weight-average molecular weight (M_(w))of the one or more glyceride copolymers in the composition ranges from8,000 g/mol to 200,000 g/mol, or from 9,000 g/mol to 100,000 g/mol, orfrom 10,000 g/mol to 30,000 g/mol, or from 11,000 g/mol to 20,000 g/mol,or from 8,000 g/mol to 20,000 g/mol, or from 9,000 g/mol to 15,000g/mol, or from 10,000 to 14,000 g/mol. In some embodiments, thepolydispersity index, as calculated as M_(w)/M_(n), of the one or moreglyceride copolymers in the composition ranges from 1.0 to 10, or from1.5 to 7, or from 2 to 6.

The composition can exist in any suitable form, such as in a singlelipid phase, or in two or more phases, such as compounds having a lipidphase and an aqueous phase. In some such embodiments, the composition isan emulsion, where the emulsion comprises an aqueous phase and anon-aqueous (oil) phase. In some embodiments, the emulsion is anoil-in-water emulsion, such that the aqueous phase serves as acontinuous phase and the oil phase serves as a discontinuous phase. Insome other embodiments, the emulsion is a water-in-oil emulsion, suchthat the oil phase serves as a continuous phase and the aqueous phaseserves as a discontinuous phase.

The compositions of any of the foregoing embodiments can, in someembodiments, also include one or more surfactants. Any suitablesurfactants can be used, such as cationic surfactants, anionicsurfactants, nonionic surfactants, or any combination thereof.

The compositions of any of the foregoing embodiments can, in someembodiments, also include one or more additives. Any suitable additivescan be used, such as carriers, solvents, co-solvents, emulsifiers,natural or synthetic colorants, natural or synthetic fragrances, naturalor synthetic deodorizers, antioxidants, corrosion inhibitors, thickeningagents, dispersants, chelating agents, precipitating agents,sequestering agents, buffers, and antimicrobial agents.

Other suitable compositions are contemplated, according to theparticular uses of the composition. In some embodiments, the compositionis not a baby care composition. In some embodiments, the composition isnot a beauty care composition. In some embodiments, the composition isnot a fabric care composition. In some embodiments, the composition isnot a home care composition. In some embodiments, the composition is nota feminine care composition. In some embodiments, the composition is nota family care composition.

Synthetic Methods

In a fifth aspect, the disclosure provides methods of forming aglyceride copolymer composition, the methods comprising: (a) providing areaction mixture comprising a metathesis catalyst and monomer compoundsof formula (IIIa):

and monomer compounds of formula (IIb):

wherein, R³¹, R³², and R³³ are independently C₁₋₂₄ alkyl orC₂₋₂₄alkenyl, each of which is optionally substituted one or more timesby —OH, provided that at least one of R³¹, R³², and R³³ is C₂₋₂₄alkenyl,which is optionally substituted one or more times by —OH; and R⁴¹, R⁴²,and R⁴³ are independently C₁₋₂₄ alkyl or C₂₋₂₄ alkenyl, each of which isoptionally substituted one or more times by —OH, provided that at leastone of R⁴¹, R⁴², and R⁴³ is 8-nonenyl, 8-decenyl, 8-undecenyl,8-dodecenyl, 8,11-dodecadienyl, 8,11-tridecadienyl,8,11-tetradecadienyl, 8,11-pentadecadienyl, 8,11,14-pentadecatrienyl,8,11,14-hexadecatrienyl, 8,11,14-heptadecatrienyl, or8,11,14-octadecatrienyl; and (b) reacting the monomer compounds offormula (IIIa) with the monomer compounds of formula (IIIb) in thepresence of the metathesis catalyst to form the glyceride polymercomposition.

The variables R³¹, R³², and R³³ can have any suitable value. In someembodiments, R³¹, R³², and R³³ are independently C₁₋₂₄ alkyl, or C₁₁₋₂₄alkyl, or C₁₃₋₂₄ alkyl, or C₁₅₋₂₄ alkyl. In some such embodiments, R³¹,R³², and R³³ are independently undecyl, tridecyl, pentadecyl, orheptadecyl. In some further such embodiments, R³¹, R³², and R³³ areindependently pentadecyl or heptadecyl. In some embodiments of any ofthe aforementioned embodiments, R³¹, R³², and R³³ are independentlyC₂₋₂₄ alkenyl, or C₉₋₂₄ alkenyl, or C₁₁₋₂₄ alkenyl, or C₁₃₋₂₄ alkenyl,or C₁₅₋₂₄ alkenyl. In some such embodiments, R³¹, R³², and R³³ areindependently 8-heptadecenyl, 10-heptadecenyl, 8,11-heptadecadienyl or8,11,14-heptadecatrienyl. In some further such embodiments, R³¹, R³²,and R³³ are independently 8-heptadecenyl, 8,11-heptadecadienyl, or8,11,14-heptadecatrienyl.

The variables R⁴¹, R⁴², and R⁴³ can have any suitable value. In someembodiments of any of the foregoing embodiments, zero, one, or two ofR⁴¹, R⁴², and R⁴³ are independently C₁₋₂₄ alkyl, or C₁₁₋₂₄ alkyl, orC₁₃₋₂₄ alkyl, or C₁₅₋₂₄ alkyl. In some such embodiments, zero, one, ortwo of R⁴¹, R⁴², and R⁴³ are independently undecyl, tridecyl,pentadecyl, or heptadecyl. In some further such embodiments, zero, one,or two of R⁴¹, R⁴², and R⁴³ are independently pentadecyl or heptadecyl.In some embodiments of any of the aforementioned embodiments, zero, one,or two of R⁴¹, R⁴², and R⁴³ are independently C₂₋₂₄ alkenyl, or C₉₋₂₄alkenyl, or C₁₁₋₂₄ alkenyl, or C₁₃₋₂₄ alkenyl, or C₁₅₋₂₄ alkenyl. Insome such embodiments, zero, one, or two of R⁴¹, R⁴², and R⁴³ areindependently 8-heptadecenyl, 10-heptadecenyl, 8,11-heptadecadienyl or8,11,14-heptadecatrienyl. In some further such embodiments, zero, one,or two of R⁴¹, R⁴², and R⁴³ are independently 8-heptadecenyl,8,11-heptadecadienyl, or 8,11,14-heptadecatrienyl.

In some other embodiments of any of the foregoing embodiments, one, two,or three of R⁴¹, R⁴², and R⁴³ are independently C₂₋₁₅ alkenyl, or C₂₋₁₄alkenyl, or C₂₋₁₃ alkenyl, or C₂₋₁₂ alkenyl, or C₅₋₁₂ alkenyl. In somesuch embodiments, one, two, or three of R⁴¹, R⁴², and R⁴³ areindependently 8-nonenyl, 8-decenyl, 8-undecenyl, 10-undecenyl,8-dodecenyl, 8,11-dodecadienyl, 8,11-tridecadienyl,8,11-tetradecadienyl, 8,11-pentadecadienyl, 8,11,14-pentadecatrienyl,8,11,14-hexadecatrienyl, 8,11,14-heptadecatrienyl, or8,11,14-octadecatrienyl. In some further such embodiments, one, two, orthree of R⁴¹, R⁴², and R⁴³ are independently 8-nonenyl, 8-decenyl,8-undecenyl, 8-dodecenyl, 8,11-dodecadienyl, 8,11-tridecadienyl,8,11-tetradecadienyl, 8,11-pentadecadienyl, 8,11,14-pentadecatrienyl,8,11,14-hexadecatrienyl, 8,11,14-heptadecatrienyl, or8,11,14-octadecatrienyl. In some further such embodiments, one, two, orthree of R⁴¹, R⁴², and R⁴³ are independently 8-nonenyl, 8-undecenyl,8,11-dodecadienyl, 8,11-tetradecadienyl, or 8,11,14-pentadecatrienyl.

The glyceride copolymers formed by the methods disclosed herein can haveany suitable molecular weight. In some embodiments of any of theaforementioned embodiments, the glyceride copolymer has a molecularweight ranging from 4,000 g/mol to 150,000 g/mol, or from 5,000 g/mol to130,000 g/mol, or from 6,000 g/mol to 100,000 g/mol, or from 7,000 g/molto 50,000 g/mol, or from 8,000 g/mol to 30,000 g/mol, or from 9,000g/mol to 20,000 g/mol.

The glyceride copolymers formed by the methods disclosed herein can haveany suitable ratio of constitutional units formed from monomer compoundsof formula (IIIa) to constitutional units formed from monomer compoundsof formula (IIIb). In some embodiments of any of the aforementionedembodiments, the number ratio of constitutional units formed frommonomer compounds of formula (IIIa) to constitutional units formed frommonomer compounds of formula (IIIb) is no more than 10:1, or no morethan 9:1, or no more than 8:1, or no more than 7:1, or no more than 6:1,or no more than 5:1, or no more than 4:1, or no more than 3:1, or nomore than 2:1, or no more than 1:1. The glyceride copolymers disclosedherein can include additional constitutional units not formed frommonomer compounds of either formula (IIIa) or formula (IIIb).

Or, in some other embodiments of any of the foregoing embodiments, thetwo or more monomers are reacted in the presence of the metathesiscatalyst as part of a reaction mixture, wherein the weight-to-weightratio of the monomer compounds of formula (IIIa) to the monomercompounds of formula (IIIb) in the reaction mixture is no more than10:1, or no more than 9:1, or no more than 8:1, or no more than 7:1, orno more than 6:1, or no more than 5:1, or no more than 4:1, or no morethan 3:1, or no more than 2:1, or no more than 1:1. In some embodiments,the reaction mixture includes additional monomer compounds besidesmonomer compounds of formula (IIIa) and formula (IIIb).

Any suitable metathesis catalyst can be used, as described in moredetail below. In some embodiments of any of the aforementionedembodiments, the metathesis catalyst is an organoruthenium compound, anorganoosmium compound, an organotungsten compound, or anorganomolybdenum compound.

The methods disclosed herein can include additional chemical andphysical treatment of the resulting glyceride copolymers. For example,in some embodiments, the resulting glyceride copolymers are subjected tofull or partial hydrogenation, such as diene-selective hydrogenation.Also, in some embodiments, the unspent metathesis catalyst and/or thespent metathesis catalyst residues are recovered. In some embodiments ofany of the foregoing embodiments, the resulting glyceride polymers aresubjected to methods that induce isomerization, such as olefinisomerization.

In another aspect, the disclosure provides methods of forming aglyceride copolymer, the methods comprising: (a) providing a reactionmixture comprising a first metathesis catalyst, unsaturated natural oilglycerides, and unsaturated alkenylized natural oil glycerides; and (b)reacting the unsaturated natural oil glycerides and unsaturatedalkenylized natural oil glycerides in the presence of the firstmetathesis catalyst to form the glyceride copolymer.

In some embodiments, the unsaturated alkenylized natural oil glycerideis formed from the reaction of a second unsaturated natural oilglyceride with a short-chain alkene in the presence of a secondmetathesis catalyst. In some such embodiments, the unsaturatedalkenylized natural oil glyceride has a lower molecular weight than thesecond unsaturated natural oil glyceride. Any suitable short-chainalkene can be used, according to the embodiments described above. Insome embodiments, the short-chain alkene is a C₂₋₈ olefin, or a C₂₋₆olefin. In some such embodiments, the short-chain alkene is ethylene,propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene,1-hexene, 2-hexene, or 3-hexene. In some further such embodiments, theshort-chain alkene is ethylene, propylene, 1-butene, 2-butene, orisobutene. In some embodiments, the short-chain alkene is ethylene. Insome embodiments, the short-chain alkene is propylene. In someembodiments, the short-chain alkene is 1-butene. In some embodiments,the short-chain alkene is 2-butene.

The first unsaturated natural oil glyceride and the second unsaturatednatural oil glyceride can be obtained from any suitable natural oilsource. In some embodiments of any of the aforementioned embodiments,the first or second unsaturated natural oil glycerides are obtained froma vegetable oil, such as a seed oil. In some further embodiments, thevegetable oil is rapeseed oil, canola oil (low erucic acid rapeseedoil), coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanutoil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil,palm kernel oil, tung oil, jatropha oil, mustard seed oil, pennycressoil, camelina oil, hempseed oil, or castor oil. In some embodiments, thevegetable oil is palm oil. In some embodiments, the vegetable oil issoybean oil. In some embodiments, the vegetable oil is canola oil.

The glyceride copolymers formed by the methods disclosed herein can haveany suitable molecular weight. In some embodiments of any of theaforementioned embodiments, the glyceride copolymer has a molecularweight ranging from 4,000 g/mol to 150,000 g/mol, or from 5,000 g/mol to130,000 g/mol, or from 6,000 g/mol to 100,000 g/mol, or from 7,000 g/molto 50,000 g/mol, or from 8,000 g/mol to 30,000 g/mol, or from 9,000g/mol to 20,000 g/mol.

The glyceride copolymers formed by the methods disclosed herein can haveany suitable ratio of constitutional units formed from the first monomerto constitutional units formed from the second monomer. In someembodiments of any of the aforementioned embodiments, the number ratioof constitutional units formed from the first monomer to constitutionalunits formed from the second monomer is no more than 10:1, or no morethan 9:1, or no more than 8:1, or no more than 7:1, or no more than 6:1,or no more than 5:1, or no more than 4:1, or no more than 3:1, or nomore than 2:1, or no more than 1:1. The glyceride copolymers disclosedherein can include additional constitutional units not formed from thefirst monomer or the second monomer.

Or, in some other embodiments of any of the foregoing embodiments, thetwo or more monomers are reacted in the presence of the metathesiscatalyst as part of a reaction mixture, wherein the weight-to-weightratio of the first monomer to the second monomer in the reaction mixtureis no more than 10:1, or no more than 9:1, or no more than 8:1, or nomore than 7:1, or no more than 6:1, or no more than 5:1, or no more than4:1, or no more than 3:1, or no more than 2:1, or no more than 1:1. Insome embodiments, the reaction mixture includes additional monomercompounds besides the first monomer and the second monomer.

Any suitable metathesis catalyst can be used as either the firstmetathesis catalyst or the second metathesis catalyst, as described inmore detail below. In some embodiments of any of the aforementionedembodiments, the first and second metathesis catalysts are anorganoruthenium compound, an organoosmium compound, an organotungstencompound, or an organomolybdenum compound.

The methods disclosed herein can include additional chemical andphysical treatment of the resulting glyceride copolymers. For example,in some embodiments, the resulting glyceride copolymers are subjected tofull or partial hydrogenation, such as diene-selective hydrogenation.

Derivation from Renewable Sources

The compounds employed in any of the aspects or embodiments disclosedherein can, in certain embodiments, be derived from renewable sources,such as from various natural oils or their derivatives. Any suitablemethods can be used to make these compounds from such renewable sources.

Olefin metathesis provides one possible means to convert certain naturaloil feedstocks into olefins and esters that can be used in a variety ofapplications, or that can be further modified chemically and used in avariety of applications. In some embodiments, a composition (orcomponents of a composition) may be formed from a renewable feedstock,such as a renewable feedstock formed through metathesis reactions ofnatural oils and/or their fatty acid or fatty ester derivatives. Whencompounds containing a carbon-carbon double bond undergo metathesisreactions in the presence of a metathesis catalyst, some or all of theoriginal carbon-carbon double bonds are broken, and new carbon-carbondouble bonds are formed. The products of such metathesis reactionsinclude carbon-carbon double bonds in different locations, which canprovide unsaturated organic compounds having useful chemical properties.

A wide range of natural oils, or derivatives thereof, can be used insuch metathesis reactions. Examples of suitable natural oils include,but are not limited to, vegetable oils, algae oils, fish oils, animalfats, tall oils, derivatives of these oils, combinations of any of theseoils, and the like. Representative non-limiting examples of vegetableoils include rapeseed oil (canola oil), coconut oil, corn oil,cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesameoil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil,jatropha oil, mustard seed oil, pennycress oil, camelina oil, hempseedoil, and castor oil. Representative non-limiting examples of animal fatsinclude lard, tallow, poultry fat, yellow grease, and fish oil. Talloils are by-products of wood pulp manufacture. In some embodiments, thenatural oil or natural oil feedstock comprises one or more unsaturatedglycerides (e.g., unsaturated triglycerides). In some such embodiments,the natural oil feedstock comprises at least 50% by weight, or at least60% by weight, or at least 70% by weight, or at least 80% by weight, orat least 90% by weight, or at least 95% by weight, or at least 97% byweight, or at least 99% by weight of one or more unsaturatedtriglycerides, based on the total weight of the natural oil feedstock.

The natural oil may include canola or soybean oil, such as refined,bleached and deodorized soybean oil (i.e., RBD soybean oil). Soybean oiltypically includes about 95 percent by weight (wt %) or greater (e.g.,99 wt % or greater) triglycerides of fatty acids. Major fatty acids inthe polyol esters of soybean oil include but are not limited tosaturated fatty acids such as palmitic acid (hexadecanoic acid) andstearic acid (octadecanoic acid), and unsaturated fatty acids such asoleic acid (9-octadecenoic acid), linoleic acid (9,12-octadecadienoicacid), and linolenic acid (9,12,15-octadecatrienoic acid).

Such natural oils, or derivatives thereof, contain esters, such astriglycerides, of various unsaturated fatty acids. The identity andconcentration of such fatty acids varies depending on the oil source,and, in some cases, on the variety. In some embodiments, the natural oilcomprises one or more esters of oleic acid, linoleic acid, linolenicacid, or any combination thereof. When such fatty acid esters aremetathesized, new compounds are formed. For example, in embodimentswhere the metathesis uses certain short-chain alkenes, e.g., ethylene,propylene, or 1-butene, and where the natural oil includes esters ofoleic acid, an amount of 1-decene and 1-decenoid acid (or an esterthereof), among other products, are formed.

In some embodiments, the natural oil can be subjected to variouspre-treatment processes, which can facilitate their utility for use incertain metathesis reactions. Useful pre-treatment methods are describedin United States Patent Application Publication Nos. 2011/0113679,2014/0275595, and 2014/0275681, all three of which are herebyincorporated by reference as though fully set forth herein.

In some embodiments, after any optional pre-treatment of the natural oilfeedstock, the natural oil feedstock is reacted in the presence of ametathesis catalyst in a metathesis reactor. In some other embodiments,an unsaturated ester (e.g., an unsaturated glyceride, such as anunsaturated triglyceride) is reacted in the presence of a metathesiscatalyst in a metathesis reactor. These unsaturated esters may be acomponent of a natural oil feedstock, or may be derived from othersources, e.g., from esters generated in earlier-performed metathesisreactions.

The conditions for such metathesis reactions, and the reactor design,and suitable catalysts are as described below with reference to themetathesis of the olefin esters. That discussion is incorporated byreference as though fully set forth herein.

Olefin Metathesis

In some embodiments, one or more of the unsaturated monomers can be madeby metathesizing a natural oil or natural oil derivative. The terms“metathesis” or “metathesizing” can refer to a variety of differentreactions, including, but not limited to, cross-metathesis,self-metathesis, ring-opening metathesis, ring-opening metathesispolymerizations (“ROMP”), ring-closing metathesis (“RCM”), and acyclicdiene metathesis (“ADMET”). Any suitable metathesis reaction can beused, depending on the desired product or product mixture.

In some embodiments, after any optional pre-treatment of the natural oilfeedstock, the natural oil feedstock is reacted in the presence of ametathesis catalyst in a metathesis reactor. In some other embodiments,an unsaturated ester (e.g., an unsaturated glyceride, such as anunsaturated triglyceride) is reacted in the presence of a metathesiscatalyst in a metathesis reactor. These unsaturated esters may be acomponent of a natural oil feedstock, or may be derived from othersources, e.g., from esters generated in earlier-performed metathesisreactions. In certain embodiments, in the presence of a metathesiscatalyst, the natural oil or unsaturated ester can undergo aself-metathesis reaction with itself.

In some embodiments, the metathesis comprises reacting a natural oilfeedstock (or another unsaturated ester) in the presence of a metathesiscatalyst. In some such embodiments, the metathesis comprises reactingone or more unsaturated glycerides (e.g., unsaturated triglycerides) inthe natural oil feedstock in the presence of a metathesis catalyst. Insome embodiments, the unsaturated glyceride comprises one or more estersof oleic acid, linoleic acid, linoleic acid, or combinations thereof. Insome other embodiments, the unsaturated glyceride is the product of thepartial hydrogenation and/or the metathesis of another unsaturatedglyceride (as described above).

The metathesis process can be conducted under any conditions adequate toproduce the desired metathesis products. For example, stoichiometry,atmosphere, solvent, temperature, and pressure can be selected by oneskilled in the art to produce a desired product and to minimizeundesirable byproducts. In some embodiments, the metathesis process maybe conducted under an inert atmosphere. Similarly, in embodiments wherea reagent is supplied as a gas, an inert gaseous diluent can be used inthe gas stream. In such embodiments, the inert atmosphere or inertgaseous diluent typically is an inert gas, meaning that the gas does notinteract with the metathesis catalyst to impede catalysis to asubstantial degree. For example, non-limiting examples of inert gasesinclude helium, neon, argon, methane, and nitrogen, used individually orwith each other and other inert gases.

The reactor design for the metathesis reaction can vary depending on avariety of factors, including, but not limited to, the scale of thereaction, the reaction conditions (heat, pressure, etc.), the identityof the catalyst, the identity of the materials being reacted in thereactor, and the nature of the feedstock being employed. Suitablereactors can be designed by those of skill in the art, depending on therelevant factors, and incorporated into a refining process such, such asthose disclosed herein.

The metathesis reactions disclosed herein generally occur in thepresence of one or more metathesis catalysts. Such methods can employany suitable metathesis catalyst. The metathesis catalyst in thisreaction may include any catalyst or catalyst system that catalyzes ametathesis reaction. Any known metathesis catalyst may be used, alone orin combination with one or more additional catalysts. Examples ofmetathesis catalysts and process conditions are described in US2011/0160472, incorporated by reference herein in its entirety, exceptthat in the event of any inconsistent disclosure or definition from thepresent specification, the disclosure or definition herein shall bedeemed to prevail. A number of the metathesis catalysts described in US2011/0160472 are presently available from Materia, Inc. (Pasadena,Calif.).

In some embodiments, the metathesis catalyst includes a Grubbs-typeolefin metathesis catalyst and/or an entity derived therefrom. In someembodiments, the metathesis catalyst includes a first-generationGrubbs-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst includes asecond-generation Grubbs-type olefin metathesis catalyst and/or anentity derived therefrom. In some embodiments, the metathesis catalystincludes a first-generation Hoveyda-Grubbs-type olefin metathesiscatalyst and/or an entity derived therefrom. In some embodiments, themetathesis catalyst includes a second-generation Hoveyda-Grubbs-typeolefin metathesis catalyst and/or an entity derived therefrom. In someembodiments, the metathesis catalyst includes one or a plurality of theruthenium carbene metathesis catalysts sold by Materia, Inc. ofPasadena, Calif. and/or one or more entities derived from suchcatalysts. Representative metathesis catalysts from Materia, Inc. foruse in accordance with the present teachings include but are not limitedto those sold under the following product numbers as well ascombinations thereof: product no. C823 (CAS no. 172222-30-9), productno. C848 (CAS no. 246047-72-3), product no. C601 (CAS no. 203714-71-0),product no. C627 (CAS no. 301224-40-8), product no. C571 (CAS no.927429-61-6), product no. C598 (CAS no. 802912-44-3), product no. C793(CAS no. 927429-60-5), product no. C801 (CAS no. 194659-03-9), productno. C827 (CAS no. 253688-91-4), product no. C884 (CAS no. 900169-53-1),product no. C833 (CAS no. 1020085-61-3), product no. C859 (CAS no.832146-68-6), product no. C711 (CAS no. 635679-24-2), product no. C933(CAS no. 373640-75-6).

In some embodiments, the metathesis catalyst includes a molybdenumand/or tungsten carbene complex and/or an entity derived from such acomplex. In some embodiments, the metathesis catalyst includes aSchrock-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst includes ahigh-oxidation-state alkylidene complex of molybdenum and/or an entityderived therefrom. In some embodiments, the metathesis catalyst includesa high-oxidation-state alkylidene complex of tungsten and/or an entityderived therefrom. In some embodiments, the metathesis catalyst includesmolybdenum (VI). In some embodiments, the metathesis catalyst includestungsten (VI). In some embodiments, the metathesis catalyst includes amolybdenum- and/or a tungsten-containing alkylidene complex of a typedescribed in one or more of (a) Angew. Chem. Int. Ed. Engl., 2003, 42,4592-4633; (b) Chem. Rev., 2002, 102, 145-179; and/or (c) Chem. Rev.,2009, 109, 3211-3226, each of which is incorporated by reference hereinin its entirety, except that in the event of any inconsistent disclosureor definition from the present specification, the disclosure ordefinition herein shall be deemed to prevail.

In certain embodiments, the metathesis catalyst is dissolved in asolvent prior to conducting the metathesis reaction. In certain suchembodiments, the solvent chosen may be selected to be substantiallyinert with respect to the metathesis catalyst. For example,substantially inert solvents include, without limitation: aromatichydrocarbons, such as benzene, toluene, xylenes, etc.; halogenatedaromatic hydrocarbons, such as chlorobenzene and dichlorobenzene;aliphatic solvents, including pentane, hexane, heptane, cyclohexane,etc.; and chlorinated alkanes, such as dichloromethane, chloroform,dichloroethane, etc. In some embodiments, the solvent comprises toluene.

In other embodiments, the metathesis catalyst is not dissolved in asolvent prior to conducting the metathesis reaction. The catalyst,instead, for example, can be slurried with the natural oil orunsaturated ester, where the natural oil or unsaturated ester is in aliquid state. Under these conditions, it is possible to eliminate thesolvent (e.g., toluene) from the process and eliminate downstream olefinlosses when separating the solvent. In other embodiments, the metathesiscatalyst may be added in solid state form (and not slurried) to thenatural oil or unsaturated ester (e.g., as an auger feed).

The metathesis reaction temperature may, in some instances, be arate-controlling variable where the temperature is selected to provide adesired product at an acceptable rate. In certain embodiments, themetathesis reaction temperature is greater than −40° C., or greater than−20° C., or greater than 0° C., or greater than 10° C. In certainembodiments, the metathesis reaction temperature is less than 200° C.,or less than 150° C., or less than 120° C. In some embodiments, themetathesis reaction temperature is between 0° C. and 150° C., or isbetween 10° C. and 120° C.

EXAMPLES

The following examples show certain illustrative embodiments of thecompounds, compositions, and methods disclosed herein. These examplesare not to be taken as limiting in any way. Nor should the examples betaken as expressing any preferred embodiments, or as indicating anydirection for further research. Unless otherwise noted, chemicals usedwere ACS, reagent, or the standard grade available from Sigma-Aldrich.

The examples below report the determination of molecular weight by gelpermeation chromatography (GPC) for certain compositions containingglyceride copolymers. Weight-average molecular weight (M_(w)) valueswere determined as follows.

Sample molecular weights were determined on an Agilent 1260 HPLC systemequipped with autosampler, column oven, and refractive index detector.The operating system was OpenLAB CDS ChemStation Workstation (A.01.03).Data storage and analysis were performed with Cirrus GPC offline,GPC/SEC Software for ChemStation, version 3.4. Chromatographicconditions are given in Table 1. In carrying out the calculation, theresults were calibrated using polystyrene reference samples having knownmolecular weights. Measurements of M_(w) values vary by 5% or less.Unless noted otherwise, the molecular weight analyses were determinedusing a chloroform mobile phase. As specifically noted below in examples6 and 7, as well as for the corresponding polystyrene calibration curve,tetrahydrofuran was used in place of chloroform as the mobile phase.

TABLE 1 Parameter Conditions Column Set Three ResiPore columns (Agilent#1113-6300) in series with guard column (Agilent #1113-1300) Particlesize: 3 μm Column dimensions: 300 × 7.5 mm Mobile Phase Chloroform FlowRate 1 mL/min, needle wash is included Column Temperature 40° C.Injection Volume 20 μL Detector Refractive Index Detector Temperature40° C.

Table 2 shows the molecular weights and the retention times of thepolystyrene standards.

TABLE 2 Standard Number Average Reported MW Retention Time (min) 1150,000 19.11 2 100,000 19.63 3 70,000 20.43 4 50,000 20.79 5 30,00021.76 6 9,000 23.27 7 5,000 23.86 8 1,000 27.20 9 500 28.48

Example 1—Reaction with Butenylized Canola Oil (BCO): Effect of BCOContent

The experimental apparatus consisted of a three-necked round-bottomflask equipped with a magnetic stir bar, a septum cap, and an outlet toa vacuum system. External heating was provided via a silicone oil bath.The septum was used to add metathesis catalyst and withdraw samples. Thevacuum system consisted of a TEFLON diaphragm pump and a pressurecontroller.

Butenylized canola oil (BCO) was made by cross-metathesizing canola oil(Wesson) with 1-butene (1 mol of 1-butene per mol of C═C double bonds inthe oil) according to the methods described in U.S. Pat. No. 8,957,268.The BCO was mixed with canola oil (Wesson) and charged to a 500-mLround-bottom flask. The oil mixture was purged with nitrogen gas(Airgas, UHP) for about 15 minutes. The reaction flask was heated toabout 70° C. and evacuated to the desired pressure (see below: 200 or450 torr absolute.) A toluene (Sigma-Aldrich, anhydrous 99.8%) solutionof C827 metathesis catalyst (10 mg/mL; Materia, Inc., Pasadena, Calif.,USA) was added to the oil mixture to achieve a catalyst level of 100ppmwt. The reaction was held at 70° C. while maintaining a dynamicvacuum at the desired pressure for 2 hours. A small sample of thereaction mixture was removed by syringe, quenched with ethyl vinyl ether(Sigma-Aldrich), and analyzed by GPC to determine the weight-averagemolecular weight (M_(w)) of the resulting glyceride oligomers.

Table 3 shows the resulting M_(w) for 13 different reactions, where thepercentage of BCO was increased. The percentage of BCO reported is aweight percentage of BCO relative to the total weight of oil (BCO andcanola oil combined). The molecular weights are reported in units ofg/mol.

TABLE 3 Percentage BCO M_(w) 450 Torr M_(w) 200 Torr (wt %) (absolute)Experiments (absolute) Experiments 0 11,700 12,300 10 12,800 13,100 3013,600 14,800 50 14,400 18,000 70 14,100 22,500 90 14,500 — 100 25,90056,600

Example 2—Reaction with Butenylized Canola Oil (BCO): Effect of ReactionTime

Using the same apparatus and procedures as those described in Example 1,50 wt %/50 wt % mixtures of BCO and canola oil were reacted for fourhours while maintaining a dynamic vacuum at either 200 or 450 torr(absolute) with samples being taken hourly. Table 4 shows the molecularweight (M_(w)) over time. The molecular weight (M_(w)) is reported inunits of g/mol.

TABLE 4 Time M_(w) M_(w) (hr) 450 Torr (absolute) Experiments 200 Torr(absolute) Experiments 1 13,600 16,100 2 13,600 18,000 3 13,100 19,000 413,000 20,000

Example 3—Cross-Metathesis of Canola Oil with Butenylized Palm Oil(BPO): Effect of Feedstock Composition

Using the same apparatus and procedures as those described in Example 1,mixtures of BPO (Wilmar) and palm oil were reacted for two hours. Table5 shows the molecular weight (M_(w)) after two hours. The molecularweight (M_(w)) is reported in units of g/mol.

TABLE 5 Percentage BPO M_(w) (wt %) 200 Torr (absolute) Experiment 159,400 25 8,100 35 5,900

Example 4—Canola Oil Self-Metathesis (Comparative Example)

Using the same apparatus (except that a two-stage rotary vane pump wasused for experiments run under dynamic vacuums of less than 10 torrabsolute and procedure described in Example 1, canola oil was reactedfor two hours. Table 6 shows the molecular weight (M_(w)) after twohours. The molecular weight (M_(w)) is reported in units of g/mol.

TABLE 6 Absolute Pressure (Torr) 100-g Scale (M_(w)) 1-kg Scale (M_(w))450 11,700 — 200 12,300 — 75 12,600 — 8 14,500 13,600 3.2 — 15,100 2.5 —15,900

A portion (473 g) of the product from the 1 kg experiment run at 2.5torr was diluted with heptane (BDH, laboratory reagent, 500 mL).Magnesol-600-R (Dallas Group of Am., 10 g) was added and the resultingmixture was stirred under nitrogen at ambient temperature for 30minutes. The Magnesol-600-R was removed by vacuum filtration. A freshcharge of Magnesol-600-R (10 g) was added and the resulting mixture wasstirred under nitrogen at ambient temperature for 30 minutes. Heptanewas removed by rotovap. Olefins were removed by vacuum distillation in a1 L three-neck round-bottom equipped with a short-path distillationhead; a condenser chilled to 5° C.; a 20 mL round bottom flask chillerwith dry-ice/isopropanol; a magnetic stir bar; and thermometers tomeasure liquid temperature and vapor temperature. Heating was suppliedthrough a resistive heating mantle. Vacuum was supplied by a two-stagerotary vane vacuum pump. The bulk of olefinic material was removed bygradually increasing the heat input. A very small nitrogen purge wasmaintained on the system for the initial part of the distillation. Thefinal pressure was about 0.1 torr absolute and the final liquidtemperature was 192° C. The olefin content was less than 1% by mass. Asample of the final product was trans-esterified with methanol andanalyzed by GC. See Table 7 (below).

Example 5—Cross-Metathesis of Canola with Butenylized Canola Oil (BCO)on One-Kilogram Scale with Catalyst Removal and Olefin Stripping

Using a similar metathesis procedure and apparatus to the one describedin Example 1, a 1 kg mixture of BCO and canola oil (50 wt %/50 wt %) wasreacted for two hours. Catalyst removal was accomplished by THMPtreatment. THMP treatments consisted of adding 1 Mtris(hydroxymethyl)phosphine (THMP, 1.0 M, 50 mol THMP/mol C827) inwater, stirring at ambient temperature for 2 hours, and then washing theproduct with water (2×100 mL) in a reparatory funnel. Olefin by-productsand traces of residual water were removed from the product by the sameprocedure and distillation apparatus as described in Example 4 exceptthat no nitrogen purge was used. The final pressure was about 0.2 torrabsolute and the final liquid temperature was 195° C. The olefin contentwas less than 1% by mass and the M_(w) of the glyceride oligomer was16,700 g/mol. A sample of the final product was trans-esterified withmethanol and analyzed by GC. See Table 7 (below).

Example 6—Cross-Metathesis of Soybean Oil with Butenylized Soybean Oil(BSO) on a Two-Kilogram Scale with Catalyst Removal and Olefin Stripping

Using the same procedure and an apparatus similar to that described inExample 1 except that a 3 L flask was used in place of the 500 mL flask,a 1 kg, 50/50 wt % mixture of butenylized soybean oil and soybean oil(Costco) was reacted for about four hours using 100 ppm wt C827 catalystafter which time the M_(w) was 11,700 g/mol. An additional 40 ppm ofcatalyst was added and after about two more hours the reaction wasquenched with ethyl vinyl ether. The M_(w) of the oligomer was 15,200g/mol using THF as the mobile phase. Olefin by-products and traces ofresidual water were removed from a 265 g sample of the product by asimilar distillation procedure and apparatus as described in Example 5.The final pressure was about 0.1 torr absolute and the final liquidtemperature was 195° C. The olefin content was less than 1% by mass. Asample of the final product was trans-esterified with methanol andanalyzed by GC. See Table 7 (below).

Example 7—Cross-Metathesis of Canola Oil with Butenylized Canola Oil(BCO) on a Twelve-Kilogram Scale with Catalyst Removal and OlefinStripping

This example was conducted in a 5 gallon Stainless Steel Reactor (Parr)equipped with an impeller, a port for air-free catalyst addition, and aStrahman valve for sampling. The reactor system was completely purgedwith nitrogen before beginning.

The BCO (6.16 kg) was produced by a procedure similar to that used inExample 1 and mixed with canola oil (6.12 kg) and charged to thereactor. The oil mixture was stirred at 200 rpm while purging withnitrogen gas for about 30 minutes through a dip tube at a rate of 0.5SCFM. The reactor was evacuated to 200 torr (absolute) and heated to 70°C. The C827 metathesis catalyst (1.0 g, Materia, Inc., Pasadena, Calif.,USA) was suspended in canola oil (50 mL) and added to the oil mixture.The reaction was maintained at 70° C. and at 200 torr for four hours atwhich time the M_(w) of the glyceride oligomers was 16,600 g/mol. Anadditional charge of C827 catalyst (0.25 g) suspended in canola oil (50mL) was added to the reaction. After an additional two hours, the M_(w)was about 17,000 g/mol and the reactor was back filled with nitrogen.

Catalyst removal was conducted in a 5 gallon jacketed glass reactorequipped with an agitator, a bottom drain valve, and ports for addingreagents. A 0.12 M aqueous solution of THMP (0.31 kg) was charged to theglass reactor and pre-heated to about 90° C. The crude metathesisreaction product, still at 70° C., was transferred to the glass reactorand the mixture was stirred (150 rpm) at about 80-90° C. for 20 minutes.The following wash procedure was done twice. Deionized water (1.9 kg at60° C.) was added to the reactor which was heated to 80-90° C. and theresulting mixture was stirred (100 rpm) for 20 minutes. The stirrer wasstopped and the reactor contents were allowed to settle for 16 hours ata constant temperature of 80-90° C. The bottom aqueous layer wascarefully drained off. Following the second wash, the washed product wascooled and then drained to a container.

The washed product was divided into two portions to remove olefins andresidual water, which was done using a similar distillation procedureand apparatus as described in Example 5. The final distillation pressurewas about 0.1 torr absolute and the final liquid temperature was about190° C. Following distillation, the two portions were recombined to givea product with M_(w) of 16,100 g/mol. A small sample of the recombinedproduct was trans-esterified with methanol and analyzed by GC. See Table7 (below)

Example 8—Diene-Selective Hydrogenation of Crude Glyceride Polymer

In a 600 mL Parr reactor, 170 g of crude metathesis product from Example6, 170 g of n-decane (Sigma-Aldrich, anhydrous, >99%), and 0.60 g PRICAT9908 (Johnson Matthey Catalysts); saturated triglyceride wax removedbefore reaction via a toluene wash) were purged with N₂, then H₂, for 15minutes each, then reacted at 160° C. under 100 psig H₂ (Airgas, UHP)with 1000 rpm stirring with a gas dispersion impeller. The H₂ pressurewas monitored and the reactor was refilled to 100 psig when it decreasedto about 70 psig. After six hours, the reaction was cooled below 50° C.and the hydrogen was displaced by nitrogen gas. The reaction mixture wasvacuum filtered through diatomaceous earth to remove the catalystsolids. Olefin by-products and n-decane were removed from the product bya similar distillation procedure and apparatus as described in Example5. The final distillation pressure was about 0.1 torr absolute and thefinal liquid temperature was 195° C. The olefin content was less than 1%by mass. A sample of the final product was trans-esterified withmethanol and analyzed by GC. The level of polyunsaturated C18 fatty acidmethyl esters (C18:2 plus C18:3) were reduced from 3.88% in the startingmaterial to 1.13% and the C21:2 diester was reduced from 6.40% in thestarting material to 3.72%.

Gas Chromatographic Analysis of Fatty Acid Residues in GlycerideCopolymer

The final glyceride oligomer products described in Examples 4, 5, 6, and7 were analyzed by gas chromatography after olefins were vacuumdistilled to below 1% by weight and the resulting oligomer products weretrans-esterified to methyl esters by the following procedure.

A sample 0.10±0.01 g was weighed into a 20 mL scintillation vial. A 1%solution of sodium methoxide in methanol (1.0 mL) was transferred bypipette into the vial and the vial was capped. The capped vial wasplaced in a sample shaker and shaken at 250 rpm and 60° C. until thesample was completely homogeneous and clear. The sample was removed fromthe shaker and 5 ml of brine solution followed by 5 ml of ethyl acetatewere added by pipette. The vial was vortex mixed for one minute tothoroughly to mix the solution thoroughly. The mixed solution wasallowed to sit until the two layers separated. The top (ethyl acetate)layer (1 mL) was transferred to a vial for gas chromatographic analysis.Their normalized compositions, based on a select group of components,are shown in Table 7 in units of wt %.

Gas chromatographic data were collected using an Agilent 6850 instrumentequipped with an Agilent DB-WAXETR column (122-7332E, 30 m×250 um×0.25um film thickness) and a Flame Ionization Detector. The methods and theconditions used are described as follows: The GC method “Fast_FAME.M”was used for the analyses of all samples in Examples 1 through 7 whilemethod “PNG_FAME.M,” with a longer run time and slightly higher finaloven temperature, was used for obtaining the data in Example 8.

Method FAST_FAME.M Method PNG_FAME.M OVEN OVEN Initial temp: 40° C. (On)Initial temp: 40° C. (On) Initial time: 0.00 min Initial time: 0.00 minRamps: Ramps: Final Final Rate Final temp time Rate Final temp time # (°C./min) (° C.) (min) # (° C./min) (° C.) (min) 1 20.00 240 20.00 1 20.00260 34.00 2 0 (Off) 2 0 (Off) Post temp: 0° C. Post temp: 0° C. Posttime: 0.00 min Post time: 0.00 min Run time: 30.00 min Run time: 45.00min Maximum temp: 260° C. Maximum temp: 260° C. Equilibration time: 0.10min Equilibration time: 0.10 min INLET (SPLIT/SPLITLESS) INLET(SPLIT/SPLITLESS) Mode: Split Mode: Split Initial temp: 250° C. (On)Initial temp: 250° C. (On) Pressure: 6.06 psi (On) Pressure: 6.06 psi(On) Split ratio: 150:1 Split ratio: 150:1 Split flow: 149.9 mL/minSplit flow: 149.9 mL/min Total flow: 157.5 mL/min Total flow: 157.5mL/min Gas saver: On Gas saver: On Saver flow: 20.0 mL/min Saver flow:20.0 mL/min Saver time: 2.00 min Saver time: 2.00 min Gas type: HydrogenGas type: Hydrogen DETECTOR (FID) DETECTOR (FID) Temperature: 300° C.(On) Temperature: 300° C. (On) Hydrogen flow: 40.0 mL/min (On) Hydrogenflow: 40.0 mL/min (On) Air flow: 450.0 mL/min (On) Air flow: 450.0mL/min (On) Mode: Constant makeup flow Mode: Constant makeup flow Makeupflow: 30.0 mL/min (On) Makeup flow: 30.0 mL/min (On) Makeup Gas Type:Nitrogen Makeup Gas Type: Nitrogen Flame: On Flame: On Electrometer: OnElectrometer: On Lit offset: 2.0 pA Lit offset: 2.0 pA COLUMN COLUMNCapillary Column Capillary Column Model Number: DB-WAXETR Model Number:DB-WAXETR Description: 122-7332E Description: 122-7332E Max temperature:260° C. Max temperature: 260° C. Nominal length: 30.0 m Nominal length:30.0 m Nominal diameter: 250.00 um Nominal diameter: 250.00 um Nominalfilm thickness: 0.25 um Nominal film thickness: 0.25 um Mode: constantflow Mode: constant flow Initial flow: 1.0 mL/min Initial flow: 1.0mL/min Nominal init pressure: 6.06 psi Nominal init pressure: 6.06 psiAverage velocity: 29 cm/sec Average velocity: 29 cm/sec Source: InletSource: Inlet Outlet: Detector Outlet: Detector Outlet pressure: ambientOutlet pressure: ambient SIGNAL SIGNAL Data rate: 20 Hz Data rate: 20 HzType: detector Type: detector Save Data: On Save Data: On INJECTORINJECTOR Sample pre-washes: 3 Sample pre-washes: 3 Sample pumps: 1Sample pumps: 1 Sample volume (uL): 1.000 Sample volume (uL): 1.000Syringe size (uL): 10.0 Syringe size (uL): 10.0 Pre washes from bottleA: 3 Pre washes from bottle A: 3 Pre washes from bottle B: 3 Pre washesfrom bottle B: 3 Post washes from bottle A: 3 Post washes from bottle A:3 Post washes from bottle B: 3 Post washes from bottle B: 3 Viscositydelay (seconds): 0 Viscosity delay (seconds): 0 Pre injection dwell(min): 0.00 Pre injection dwell (min): 0.00 Post injection dwell (min):0.00 Post injection dwell (min): 0.00 Sample skim depth (mm): 0.0 (Off)Sample skim depth (mm): 0.0 (Off) NanoLiter Adapter Installed NanoLiterAdapter Installed Solvent Wash Mode: A, B Solvent Wash Mode: A, BPlunger Speed: Fast Plunger Speed: Fast Solvent saver: Off Solventsaver: Off

TABLE 7 Fatty Acid Example 4 Example 5 Example 6 Example 7 Methyl EsterProduct Product Product Product Component (wt %) (wt %) (wt %) (wt %)C10:1 — 6.72 2.97 4.58 C12:1 1.74 7.33 4.77 6.25 C13:2 — 1.33 0.71 0.72C15:1 8.53 5.05 12.21 5.05 C16:0 5.89 6.12 14.69 5.65 C16:1 1.97 1.080.43 1.06 C18:0 2.53 2.65 6.05 2.58 C18:1 35.87 19.52 6.31 19.80 C18:20.80 1.33 3.46 0.89 C18:3 0.64 0.39 0.42 0.27 C20:0 1.30 0.85 0.48 0.90C20:1 2.10 1.08 0.29 1.15 C21:2 2.82 3.59 1.76 3.61 C22:0 0.53 0.56 0.080.60 C18:1 diester 26.80 29.10 21.84 29.85 C20:1 diester 3.09 3.11 1.023.08 C21:2 diester 1.00 5.10 6.40 4.95

What is claimed is:
 1. A method of forming a glyceride copolymer, themethod comprising: (a) providing a reaction mixture comprising a firstmetathesis catalyst, unsaturated natural oil glycerides, and unsaturatedalkenylized natural oil glycerides, wherein the number ratio ofconstitutional units formed from the unsaturated natural oil glyceridesto constitutional units formed from the unsaturated alkenylized naturaloil glycerides is no more than 10:1; and (b) reacting the unsaturatednatural oil glycerides and unsaturated alkenylized natural oilglycerides in the presence of the first metathesis catalyst to form theglyceride copolymer.
 2. The method of claim 1, wherein the unsaturatedalkenylized natural oil glycerides are formed from the reaction ofunsaturated natural oil glycerides with a short-chain alkene in thepresence of a second metathesis catalyst.
 3. The method of claim 2,wherein the short-chain alkene is selected from the group consisting ofethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene,2-pentene, 1-hexene, 2-hexene, and 3-hexene.
 4. The method of claim 3,wherein the short-chain alkene is selected from the group consisting ofethylene, propylene, 1-butene, 2-butene, and isobutene.
 5. The method ofclaim 4, wherein the short-chain alkene is ethylene.
 6. The method ofclaim 4, wherein the short-chain alkene is propylene.
 7. The method ofclaim 4, wherein the short-chain alkene is 1-butene.
 8. The method ofclaim 4, wherein the short-chain alkene is 2-butene.
 9. The method ofclaim 1, wherein the unsaturated natural oil glycerides are obtainedfrom a natural oil.
 10. The method of claim 9, wherein the unsaturatednatural oil glycerides are obtained from a vegetable oil.
 11. The methodof claim 10, wherein the vegetable oil is selected from the groupconsisting of rapeseed oil, canola oil (low erucic acid rapeseed oil),coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanut oil,safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil, palmkernel oil, tung oil, jatropha oil, mustard seed oil, pennycress oil,camelina oil, hempseed oil, and castor oil.
 12. The method of claim 1,wherein the glyceride copolymer has a number average molecular weightranging from 4,000 g/mol to 150,000 g/mol.
 13. The method of claim 1,wherein the first metathesis catalyst is selected from the groupconsisting of an organoruthenium compound, an organoosmium compound, anorganotungsten compound, and an organomolybdenum compound.
 14. Themethod of claim 1, wherein the second metathesis catalyst is selectedfrom the group consisting of an organoruthenium compound, anorganoosmium compound, an organotungsten compound, and anorganomolybdenum compound.